CN107108816A

CN107108816A - Water based pressure sensitive adhesive composition

Info

Publication number: CN107108816A
Application number: CN201580071843.3A
Authority: CN
Inventors: 郄丽丽; 陈中; 宋志鹏; J·R·雅各布森; J·塞斯
Original assignee: 3M Innovative Properties Co
Current assignee: 3M Innovative Properties Co
Priority date: 2014-12-30
Filing date: 2015-12-14
Publication date: 2017-08-29
Anticipated expiration: 2035-12-14
Also published as: US20180265754A1; EP3240811A1; JP2018506616A; EP3240811B1; CN107108816B; KR20170093989A; JP6258565B1; US10081745B1; WO2016109174A1; KR101795349B1

Abstract

The invention provides a kind of contact adhesive, the contact adhesive is the desciccate of latex composition, and the latex composition is formed by emulsion compositions.Additionally provide the latex composition and the emulsion compositions.The emulsion compositions have drop, and the drop includes various monomers and (methyl) acrylate polymer being dissolved in the monomer.In addition, the invention provides a kind of product including the pressure sensitive adhesive layer and the method for forming the contact adhesive.The contact adhesive usually has high peel adhesion and high shear strength (that is, high cohesive strength or high shear confining force).

Description

Water based pressure sensitive adhesive composition

The cross reference of related application

The U.S. Provisional Patent Application No.62/097784 submitted this application claims on December 30th, 2014 rights and interests, this is special The disclosure of profit is incorporated by herein.

Technical field

Latex composition the invention provides a kind of contact adhesive, for forming contact adhesive and for shape Into the emulsion compositions of latex composition.

Background technology

Contact adhesive (PSA) adhesive tape is almost omnipresent in house and workplace.By its simplest construction One, pressure sensitive adhesive tape includes back sheet and is attached to the adhesive phase of back sheet.According to pressure sensitive adhesive tape association (Pressure- Sensitive Tape Council), it is known that contact adhesive, which has, includes following property：(1) strong and lasting adhesion Power；(2) it is that can be adhered with the pressure no more than finger pressure；(3) there is the ability being enough to be maintained on attachment；And (4) are enough Cohesive strength to make it be cleanly removed from attachment.It has been found that the material played one's part to the full as PSA is included through setting Meter and prepare with viscoelastic polymer needed for showing, the viscoplasticity realize desired adhesion strength, peel adhesion with Shear the balance of confining force.PSA is characterised by that generally under room temperature (for example, about 20 DEG C to 25 DEG C) be tacky.Only have Material that is sticky or only adhering to certain surface not necessarily constitutes PSA；Term PSA is covered with other viscoelastic material.

Contact adhesive based on acrylic acid is widely used.These pressure-sensitive adhesive compositions can use organic solvent Prepare, can also be prepared without organic solvent.Although the PSA composition comprising organic solvent is currently commercially occupied predominantly Position, but be due to various problems pollution, high energy consumption and the inflammability associated such as with using organic solvent so that its importance Gradually reduce.That is, adhesives industry increasingly focuses on that organic solvent content is low or adhesive composition without organic solvent.

Some such adhesive compositions can be with for example, water-based latex composition enters as formed by by emulsion polymerization It is prepared by row.Such adhesive is described in, for example, United States Patent (USP) 5,686,518 (Fontenot et al.), United States Patent (USP) 6,710, 128 (Helmer et al.), United States Patent (USP) 6,511,744 (Centner et al.), United States Patent (USP) 6,048,611 (Lu et al.), the U.S. Patent 4,912,169 (Whitmire et al.), United States Patent (USP) 6,657,011 (Lau et al.), United States Patent (USP) 8,258,240 (Suzuki et al.) and U.S. Patent Application Publication 2010/0081764 (Ouzineb et al.).

The content of the invention

The invention provides a kind of contact adhesive, the contact adhesive is the desciccate of latex composition, the latex Composition is formed by emulsion compositions.Additionally provide latex composition and emulsion compositions.In addition, the invention provides include this The product of contact adhesive and the method for forming the contact adhesive.Contact adhesive is in room temperature (for example, about 20 DEG C to about 25 DEG C) and high temperature (for example, about 70 DEG C or so) under there is the flat of good peel adhesion and shear strength (that is, cohesive force) Weighing apparatus, when especially adhering to low-surface-energy substrate.

In first aspect there is provided emulsion compositions, the emulsion compositions include a) water, and radical polymerization can be carried out by b) having The polymerisable surfactant of the unsaturated group of conjunction, c) the first monomer composition, and d) second (methyl) acrylate gathers Compound.First monomer composition includes (methyl) alkyl acrylate that straight or branched alkyl group has at least six carbon atoms Ester.Based on the total monomer weight of the first monomer composition, the second (methyl) acrylate polymer is with 0.5 weight % to 15 weights The amount for measuring % is present, and its glass transition temperature is more than or equal to 50 DEG C.Second (methyl) acrylate polymer is by Two monomer compositions are formed, and based on the gross weight meter of monomer in second comonomer composition, the second comonomer composition is comprising at least 50 weight % (methyl) acrylate ester, wherein group of naphthene base have at least six carbon atoms.Emulsion compositions are included First phase and the second phase, first mutually include water, and second as droplet distribution in the first phase.Drop includes following item Mixture：I) at least 90 weight % the first monomer composition；And ii) second (methyl) acrylate polymer.Second (first Base) acrylate polymer can not be miscible with the first phase, and in the first monomer composition being dissolved in drop.

In second aspect there is provided latex composition, reaction product of the latex composition comprising emulsion compositions is (i.e., Polymerizate), wherein latex composition includes polymeric latex particles.Emulsion compositions are same as above.

In the third aspect there is provided contact adhesive, the contact adhesive is the desciccate of latex composition.Latex group Compound includes the reaction product (that is, polymerizate) of emulsion compositions, and wherein latex composition includes polymeric latex particles.Emulsion Composition is same as above.

In fourth aspect, there is provided product.The product includes substrate and the first pressure sensitive adhesive layer, the first contact adhesive First main surface positioning (and directly or indirectly adhering to the first main surface of substrate) of layer adjacent substrate.Pressure sensitive adhesive layer It is the desciccate of latex composition.Latex composition includes the reaction product (that is, polymerizate) of emulsion compositions, wherein glue Newborn composition includes polymeric latex particles.Emulsion compositions are same as above.

At the 5th aspect, the invention provides the method for forming contact adhesive.This method includes：A) form as described above Emulsion compositions；B) emulsion compositions polymerization is made to form the latex composition for including polymeric latex particles；And c) dry Latex composition is to form contact adhesive.

Brief description of the drawings

Fig. 1 is modulation system differential scanning calorimetric curve of the polymeric latex particles in the second heating (2H) cycle of embodiment 1 Figure.Hot-fluid is drawn as the temperature funtion in blanket of nitrogen.

Fig. 2 is modulation system differential scanning calorimetric curve of the polymeric latex particles in the second heating (2H) cycle of embodiment 2 Figure.Hot-fluid is drawn as the temperature funtion in blanket of nitrogen.

Embodiment

The invention provides contact adhesive, the contact adhesive is the desciccate of latex composition, latex composition Formed by emulsion compositions.Additionally provide latex composition and emulsion compositions.Emulsion compositions, which have, is suspended in predominantly water The first phase in drop.Drop includes various monomers and (methyl) acrylate polymer being dissolved in monomer.Make breast The content polymerization of drop in liquid composition, to form polymeric latex particles in latex composition.Contact adhesive passes through dry The dry latex composition is provided.In addition, the invention provides the product including pressure sensitive adhesive layer and forming pressure-sensitive adhesion The method of agent.

Contact adhesive usually has good between peel strength and shear strength (that is, cohesive strength or shearing confining force) Good balance, especially when adhering on lower-surface-free-energy surface.Prepare with the pressure-sensitive of so good adhesive properties balance Adhesive can be challenging.The increase of peel strength is frequently accompanied by the reduction of shear strength, and the increasing of shear strength Plus it is frequently accompanied by the reduction of peel strength.Second (methyl) acrylate polymer is added in emulsion compositions contributes to shape Into the contact adhesive with the balance between improved peel strength and shear strength.I.e., it is possible to keep good stripping Improve shear strength while intensity (or not damaging peel strength excessively), and can keep good shear strength (or Do not damage shear strength excessively) while improve peel strength.

As used herein, term " polymer " " and " polymerization " and " polymeric material " are used interchangeably to refer to homopolymerization Thing, copolymer, terpolymer etc..

As used herein, term " (methyl) acrylate " be both methacrylate and acrylate monomer, by Polymeric material that these monomer deriveds go out, or both.Similarly, term " (methyl) acrylic acid " refer to acryhic material and Both methacrylic materials, term " (methyl) acrylamide " refers to both acrylamide and Methacrylamide, and art Language " (methyl) acrylonitrile " refers to both methacrylonitrile and acrylonitrile.

As used herein, term " (methyl) acrylate polymer " refers to by one or more ethylenically unsaturated monomers The polymeric material of formation, wherein the monomer more than 50 weight % has ethylenic unsaturated group, the ethylenic unsaturated group Group is (methyl) acryloyl group with following formula：H2C=CR^a- (CO)-, wherein R^aFor hydrogen or methyl, and-(CO)-it is carbonyl Base group.Some exemplary (methyl) acrylate polymers are formed by monomer composition, and these monomer compositions, which have, to be more than 60 weight %, more than 70 weight %, more than 80 weight %, more than 90 weight %, more than 95 weight %, more than 98 weight % or The monomer with (methyl) acryloyl group more than 99 weight %.Weight % is based on gathering for forming (methyl) acrylate The gross weight meter of monomer in the monomer composition of compound.

Term " glass transition temperature " or " Tg " refer to material from the temperature that glassy transition is rubbery state.Above and below herein Wen Zhong, term " glassy state " means that material is hard and frangible (and therefore relatively easy broken), and term " rubbery state " means material Material is flexible and flexible.For polymeric material, Tg is the critical-temperature for separating its glassy state and rubbery state.If Polymeric material is in the temperature less than its Tg, then large-scale molecular motion is just severely limited, because the material is Substantially freeze.On the other hand, if polymeric material is in the temperature higher than its Tg, then molecular motion repeats single with it The scale of member occurs, so as to allow material to be soft or rubbery state.Any Tg for referring to monomer herein refers both to thus single The Tg of the homopolymer of body formation.The glass transition temperature of polymeric material usually using such as differential scanning calorimetry (for example, Modulated Differential Scanning Calorimetry) method determine.Alternatively, if the amount of every kind of monomer for forming polymeric material With Tg, it is known that then Fox formula can be used to calculate for the glass transition of polymeric material.

When mentioning scope, range endpoints are understood to include in scope.For example, expression is " in the scope from x to y It is interior ", " in the range of x to y ", " in the amount from x to y ", " in x to y amount " or similar expression include end value x and y。

As used herein, term "and/or", such as express A and/or B in "and/or" refer to single A, single B, Both or A and B.

Emulsion compositions are used to form latex composition, and contact adhesive is finally included：A) water, b) having to be carried out The polymerisable surfactant of the unsaturated group (for example, ethylenic unsaturated group) of Raolical polymerizable, c) first is single Body composition, and d) second (methyl) acrylate polymer.Emulsion has the first phase and the second phase, and first mutually includes water, Second as droplet distribution in the first phase.Polymerisable surfactant it is generally main (for example, at least 95 weight % or with Upper, at least 97 weight %, at least 98 weight %, at least 99 weight %, at least 99.5 weight %, at least 99.8 weight % or extremely Few 99.9 weight %) it is present in the interface in the first phase and/or between drop and the first phase.Second (methyl) acrylate gathers Compound is dissolved in the monomer of the first monomer composition, and monomer is in the drop of the second phase of emulsion compositions.Second (first Base) first phase of the acrylate polymer generally with emulsion compositions can not be miscible.Second (methyl) acrylate polymer by Second comonomer composition is formed, and the second comonomer composition is different from the first monomer composition contained in emulsion compositions.

The key component of emulsion compositions is water.The solid % of emulsion compositions is at most usually 70 weight % or higher, Such as at most 75 weight %.If solid % is higher, the viscosity of emulsion may be too high to make drop is fully dispersed to open.One In a little embodiments, solid % is at most 65 weight %, at most 60 weight %, at most 55 weight % or at most 50 weight %.Gu Body % is generally at least 10 weight %.If solid is less, preparing the efficiency of latex particle low may obtain and can not receive.One In a little embodiments, solid % is at least 15 weight %, at least 20 weight %, at least 25 weight %, at least 30 weight %, at least 35 weight %, at least 40 weight % or at least 45 weight %.In some instances, solid % is in 10 weight % to 75 weight % In the range of, in the range of 10 weight % to 70 weight %, in the range of 20 weight % to 70 weight %, in 30 weight % In the range of to 70 weight %, in the range of 40 weight % to 70 weight % or in 40 weight % to 60 weight % scope It is interior.Gross weight meters of the solid % based on emulsion compositions.

It is not the part emulsion compositions usually water of solid.Therefore, the water content of emulsion usually from least 25 weights Measure % or at least 30 weight %.In some embodiments, water content can be at most 90 weight %, at most 85 weight %, extremely Many 80 weight %, at most 75 weight %, at most 70 weight %, at most 65 weight %, at most 60 weight % or at most 55 weights Measure %.Water content can be at least 35 weight %, at least 40 weight %, at least 45 weight % or at least 50 weight %.At some In example, water content is in following scope：25 weight % to 90 weight %, 30 weight % are to 90 weight %, 30 weight % to 80 Weight %, 30 weight % are to 70 weight %, 30 weight % to 60 weight % or 40 weight % to 60 weight %.The amount of water is based on The gross weight meter of emulsion compositions.

A part of water can be substituted with the insoluble polar organic solvent (such as, polar solvent) for being mixed in water.If there is If, it is mutually not no more than 20 weight %, no more than 15 weight %, no more than 10 weight % or no more than the first of 5 weight % The solvable polar organic solvent for being mixed in water.Polar solvent usually from alcohol, such as with 1 to 10 carbon atom, 1 to 6 carbon atom, Or the alcohol of 1 to 4 carbon atom.In many embodiments, not purposefully by the insoluble polar organic solvent for being mixed in water It is added in emulsion compositions, but it can be present in a kind of component in other components as pollutant or diluent.

Emulsion compositions include polymerisable surfactant.As used herein, term " polymerisable surfactant " refers to Surfactant with polymerizable groups, the group is that can carry out the unsaturated group of Raolical polymerizable.In emulsion group In compound, polymerisable surfactant be generally in the first phase and/or first mutually between the drop that is suspended in the first phase Interface.Polymerisable surfactant advantageously forms the latex composition with good stability (for example, polymeric latex is closed Particle remains suspension, and does not coalesce).During the polymerisation of emulsion compositions, polymerisable surfactant can be with Become a part for polymeric latex particles.

Using polymerisable surfactant rather than the surfactant without polymerizable groups often improve gained The peel strength and shear strength of contact adhesive.Under high humidity conditions, the surfactant without polymerizable groups is past Toward the surface for moving to contact adhesive.There is surfactant on the surface of contact adhesive can reduce contact adhesive Adhesive properties.On the contrary, polymerisable surfactant can polymerize with the monomer in the first monomer composition, and become polymeric gel A part for milk particle.Aggregate into the mobility of polymeric latex particles often limiting surface activating agent.

Exemplary polymerisable surfactant includes：Acrylic polyoxyethylene alkylphenyl compound, such as with trade name NOIGEN RN (for example, RN-10, RN-20, RN-30, RN-40 and RN-5065) are from Russia of the U.S. carat He Ma Zhou Tulsas Those commercially available compounds of Montello companies (Montello, Inc., Tulsa, OK, USA), it has knot as shown below Structure, wherein n are at least 2, and wherein x is integer, such as integer close or equal to 9.

Other examples polymerisable surfactant includes：Acrylic polyoxyethylene alkyl phenyl ether ammonium sulfate compound, Such as with trade name HITENOL BC (for example, BC-10, BC-1025, BC-20, BC-2020 and BC-30) from Montello companies Those (Montello, Inc.) commercially available compounds, it has structure as shown below, and wherein n is at least 2, and wherein x For integer, such as integer close or equal to 9.

Another exemplary polymerisable surfactant is Sodium Dodecyl Allyl Sulfosuccinate, CH₃-(CH₂)₁₁- O-(CO)-CH₂-CH(SO₃Na)-(CO)-O-CH₂- CH=CH₂, it can be cut down with trade name TREM LF40 from Germany north Lai Yinxi In sub- Kening Co., Ltd (Cognis Corporation, North Rhime-Westphalia, Germany) it is commercially available.Separately One exemplary polymerisable surfactant is phosphate, such as with trade name MAXENUL (for example, MAXEMUL 6106 and 6112) From the commercially available phosphate of the Croda companies (Croda (Edison, NY, USA)) of USA New York Edison.

Polymerisable surfactant is generally with most about 2 weight %, at most 1.8 weight % or at most 1.5 weight % amount Use.The amount of polymerisable surfactant is generally at least 0.5 weight %, at least 0.7 weight %, or at least 1 weight %.Weight Measure gross weight meters of the % based on monomer in the first monomer composition.

Emulsion compositions include the first monomer composition.First monomer composition is generally selected so that the first monomer group The polymerizate (be referred to as " first (methyl) acrylate polymer ") of compound have no more than 20 DEG C, be not more than 10 DEG C, less In 0 DEG C, no more than -10 DEG C or no more than -20 DEG C of glass transition temperature.

The first monomer composition in emulsion compositions generally includes the straight or branched with the carbon atom of band at least six (methyl) alkyl acrylate of alkyl group.In many embodiments, other optional monomers can be included, precondition is poly- Closing product has sufficiently low glass transition temperature.Select the amount and type of any optional monomers so that the first combination of monomers In thing at least 90 weight % monomer be in be dispersed within the drop in the first phase of emulsion compositions.With band at least six (methyl) alkyl acrylate monomer of the straight or branched alkyl group of carbon atom is likely to have low dissolving in the first phase Degree, and it is likely to main (for example, at least 95 weight % or more, at least 97 weight %, at least 98 weight %, at least 99 weights Measure %, at least 99.5 weight %, at least 99.8 weight % or at least 99.9 weight %) it is in drop, the droplet distribution is the In one phase.If optional polar monomer or other optional monomers are included in hydrophobicity than the straight chain with the carbon atom of band at least six Or in worse first monomer composition of (methyl) alkyl acrylate monomer of branched alkyl group, then with band at least six (methyl) alkyl acrylate monomer of the straight or branched alkyl group of individual carbon atom is compared, and these optional monomers are in water The solubility of (for example, in first phase) may be higher.With polymerizeing in drop, in the first phase in these optional monomers one A little monomers can be penetrated into drop, and become a part for formed polymeric latex particles.

(methyl) alkyl acrylate in first monomer composition has the straight or branched of the carbon atom of band at least six Alkyl group.Alkyl group has (methyl) the alkyl acrylate monomer hydrophobicity for being less than six carbon atom smaller, and not It may be primarily present in drop very much.In some embodiments, alkyl group can have at least eight carbon atom, at least ten Carbon atom or at least 12 carbon atoms.The alkyl group of (methyl) alkyl acrylate can have at most 28 carbon atoms or with Upper, at most 24 carbon atoms, at most 20 carbon atoms or at most 18 carbon atoms.In many embodiments, especially when carbon is former When subnumber is more than 12, alkyl group is branched group.If alkyl group is straight chain group, with more than 12 carbon atoms Some (methyl) alkyl acrylates of alkyl group are crystallizable.In emulsion compositions, (methyl) alkyl acrylate is not required to Crystallize.

With the carbon atom of band at least six it is straight or branched alkyl group, for the example in the first monomer composition Property (methyl) alkyl acrylate monomer includes but is not limited to：The just own ester of acrylic acid, acrylic acid 4- methyl -2- amyl groups ester, propylene Sour 3- methylpents base ester, acrylic acid 2- ethyl-butyls ester, 2-ethylhexyl acrylate, acrylic acid 2- methylhexyl esters, propylene Sour n-octyl, Isooctyl acrylate monomer, acrylic acid 2- monooctyl esters, the different nonyl ester of acrylic acid, isoamyl acrylate, the positive last of the ten Heavenly stems ester of acrylic acid, third Olefin(e) acid isodecyl ester, acrylic acid 2- propylheptyls ester, the different tridecane ester of acrylic acid, acrylic acid isooctadecane ester, acrylic acid 2- octyl groups Decyl ester, lauryl ester, acrylic acid heptadecane ester, the just own ester of methacrylic acid, isodecyl methacrylate, methyl-prop Olefin(e) acid 2- ethylhexyls, EHMA and lauryl ester.

With the carbon atom of band at least six it is straight or branched alkyl group, for other in the first monomer composition (methyl) alkyl acrylate has formula (I).

In formula (I), group R³For hydrogen or methyl, and group R¹And R²It is each independently with 4 to 14 carbon atoms Straight or branched alkyl group.These monomers are usually formed by Guerbet alcohol, and Guerbet alcohol is 2- alkyl chain triacontanols.Have The exemplary monomer of formula (I) includes：Acrylic acid 2- butyl octyls ester, acrylic acid 2- butyl decyl ester, acrylic acid 2- hexyl octyl groups Ester, acrylic acid 2- hexyls decyl ester, the stearyls of acrylic acid 2- 14, the hexacosane base esters of acrylic acid 2- ten, acrylic acid 2- Decyl tetradecane base ester, acrylic acid 2- octyldodecyls, acrylic acid 2- hexyls decyl ester, acrylic acid 2- octyl-decyls ester, Acrylic acid 2- hexyls dodecyl ester and acrylic acid 2- octyldodecyls.

First monomer composition generally comprises at least 50 weight % straight or branched with the carbon atom of band at least six (methyl) alkyl acrylate of alkyl group.First monomer composition usually comprising at least 60 weight %, at least 70 weight %, Or (methyl) alkyl acrylate of at least 80 weight % straight or branched alkyl group with the carbon atom of band at least six. The amount of (methyl) alkyl acrylate of the alkyl group with the carbon atom of band at least six can be at most 100 weight %.The One monomer composition usually has band at least six comprising at most 95 weight %, at most 90 weight % or at most 85 weight % (methyl) alkyl acrylate of the straight or branched alkyl group of carbon atom.In some embodiments, (methyl) acrylic acid The amount of Arrcostab is in the range of 50 weight % to 100 weight %, in the range of 50 weight % to 95 weight %, in 60 weights To 90 weight %'s in the range of amount % to 95 weight %, in the range of 70 weight % to 95 weight % or in 75 weight % In the range of.Gross weight meter of the amount of (methyl) alkyl acrylate based on monomer in the first monomer composition.

In some embodiments, by (methyl) third of the straight or branched alkyl group with the carbon atom of band at least six Olefin(e) acid Arrcostab is combined with optional (methyl) the acrylate ester in the first monomer composition.As used herein, term " cycloalkanes Base " refers to monocyclic alkyl, bicyclic alkyl or tricyclic alkyl group.The example of (methyl) acrylate ester monomer is included but not It is limited to：(methyl) isobornyl acrylate, (methyl) acrylic acid 3,3,5- 3-methyl cyclohexanols ester, (methyl) cyclohexyl acrylate, (methyl) acrylic acid Buddha's warrior attendant alkyl ester, (methyl) acrylic acid 3,5- dimethyladamantanes ester and (methyl) acrylic acid 4- tert-butyl groups Cyclohexyl.

Some in these (methyl) acrylate esters have high glass-transition temperature (such as, at least 80 DEG C), and And consumption must lack enough so that the polymerizate of the first monomer composition has no more than 20 DEG C of glass transition temperature. The presence of (methyl) acrylate ester can strengthen the molten of second (methyl) acrylate polymer in the first monomer composition Xie Du.In many embodiments comprising optional (methyl) acrylate ester, the first monomer composition includes at least 0.5 weight Measure %, at least 1 weight %, at least 2 weight %, at least 5 weight % or at least 10 weight % (methyl) acrylate ester. The amount of (methyl) acrylate ester can be up to 30 weight %, at most 25 weight %, at most 20 weight % or at most 15 weights Measure %.For example, the amount of (methyl) acrylate ester in the first monomer composition can be in following scope：0 weight % is extremely 30 weight %, 1 weight % are to 30 weight %, 0 weight % to 20 weight %, 1 weight % to 20 weight % or 5 weight % to 20 Weight %.Gross weight meter of the percentage by weight of (methyl) acrylate ester based on monomer in the first monomer composition.

First monomer composition optionally includes polar monomer, and such as, optional acidiferous monomer is (that is, with acidic groups The monomer of group) or optional hydroxyl monomer (that is, the monomer with oh group).These optional monomers can be added to increase The cohesive strength of final polymeric material.Suitable optionally acidiferous monomer includes but is not limited to：(methyl) acrylic acid, itaconic acid, (it is hydrolyzed with two carboxylic acids for maleic acid, 2- carboxyethyl acrylates, crotonic acid, citraconic acid, maleic acid, maleic anhydride Group), oleic acid and mono succinate -2- acryloyloxyethyl esters.Suitable optionally hydroxyl monomer includes but is not limited to：Hydroxyl Alkyl (methyl) acrylate is (for example, (methyl) acrylic acid 2- hydroxyl ethyl esters, (methyl) acrylic acid 2- hydroxypropyl acrylates, (methyl) propylene Sour 3- hydroxypropyl acrylates and (methyl) acrylic acid 4- hydroxy butyl esters) or hydroxyalkyl (methyl) acrylamide (for example, 2- ethoxy (first Base) acrylamide or 3- hydroxypropyls (methyl) acrylamide).In many embodiments, polar monomer is acid monomer. In many embodiments, optional polar monomer has (methyl) acryloyl group.First monomer composition generally comprises 0 weight Measure % to 15 weight %, 0.5 weight % to 15 weight %, 1 weight % to 15 weight %, 0 weight % to 10 weight %, 0.5 weight Measure % to 10 weight %, 1 weight % to 10 weight %, 0 weight % to 5 weight %, 0.5 weight % to 5 weight % or 1 weight Measure % to 5 weight % optional polar monomer.The amount of optional polar monomer used is selected so that in the first monomer composition At least 85 weight % monomer is within the drop of the second phase.Percentage by weight based in the first monomer composition monomer it is total Weight meter.

First monomer composition optionally may comprise up to the 20 weight % alkyl base with one to five carbon atom of band (methyl) alkyl acrylate of group.Alkyl group can be straight chain or side chain.If using it is a greater amount of have band one to (methyl) alkyl acrylate of the alkyl group of five carbon atoms, then may have in the first monomer composition entirety and be in too much In first phase rather than in drop.In many embodiments, (methyl) of the alkyl group with one to five carbon atom of band The amount of alkyl acrylate is not more than 15 weight %, is not more than 10 weight % or no more than 5 weight %.In some implementations In scheme, in the absence of (methyl) alkyl acrylate of the alkyl group with one to five carbon atom of band.In other embodiment party In case, the first monomer composition can include at least 0.5 weight %, at least 1 weight %, at least 2 weight % or at least 5 weight % The alkyl group with one to five carbon atom of band (methyl) alkyl acrylate.Alkane with one to five carbon atom of band The amount of (methyl) alkyl acrylate of base group is generally in following scope：0 weight % to 20 weight %, 1 weight % to 20 Weight %, 5 weight % are to 20 weight %, 10 weight % to 20 weight %, 0 weight % to 15 weight %, 1 weight % to 15 weights Measure %, 5 weight % to 15 weight %, 0 weight % to 10 weight %, 1 weight % to 10 weight %, 0 weight % to 5 weight %, Or 1 weight % to 5 weight %.Gross weight meter of the amount of (methyl) alkyl acrylate based on monomer in the first monomer composition.

First monomer composition can comprising straight chains of the 50 weight % to 100 weight % with the carbon atom of band at least six or (methyl) alkyl acrylate, 0 weight % to 30 weight % (methyl) acrylate ester, 0 weight of branched alkyl group Measure (methyl) alkyl acrylate and 0 weight of % to the 20 weight % alkyl group with one to five carbon atom of band Measure % to 15 weight % polar monomer.In some instances, the first monomer composition includes 60 weight % to 98 weight %'s (methyl) alkyl acrylate, the 1 weight % to 25 weights of straight or branched alkyl group with the carbon atom of band at least six Measure % (methyl) acrylate ester, 0 weight % to the 15 weight % (first with one to five atom alkyl groups of band Base) alkyl acrylate and 1 weight % to 15 weight % polar monomer.In some instances, the first monomer composition bag (methyl) acrylic acid of the straight or branched alkyl group with the carbon atom of band at least six containing 70 weight % to 98 weight % Arrcostab, 1 weight % to 20 weight % (methyl) acrylate ester, 0 weight % to 10 weight % have a band one to five The polar monomer of (methyl) alkyl acrylate of individual atom alkyl groups and 1 weight % to 10 weight %.

In other examples, the first monomer composition has the carbon of band at least six former comprising 60 weight % to 98 weight % (methyl) alkyl acrylate, 1 weight % to 30 weight % (methyl) acrylic acid ring of the straight or branched alkyl group of son The polar monomer of alkyl ester and 1 weight % to 10 weight %.For example, the first monomer composition includes 70 weight % to 98 weights Measure % (methyl) alkyl acrylate of the straight or branched alkyl group with the carbon atom of band at least six, 1 weight % extremely 20 weight % ring (methyl) acrylate and 1 weight % to 10 weight % polar monomer such as (methyl) acrylic acid.

Emulsion compositions have scattered drop in the first phase.Emulsion compositions polymerization with formed latex composition it Before, drop includes second (methyl) acrylate polymer solution being dissolved in the component of the first monomer composition, these groups Office is in drop.Generally, at least 90 weight % monomer is in the drop of emulsion in the first monomer composition, and first It is not more than 10 weight % monomer in composition to be in the first phase of emulsion compositions.Hydrophobicity, which is less than, has band at least six The polar monomer or other monomers of (methyl) alkyl acrylate of the straight or branched alkyl group of carbon atom can be distributed in In drop and the first phase.With proceeding for polymerization, arbitrarily hydrophobicity list less in these polar monomers or the first phase Body can spread in drop, and become a part for polymeric latex particles.In some embodiments, the first monomer composition In at least 92 weight %, at least 95 weight %, at least 98 weight % or at least 99 weight % monomer is in emulsion compositions In drop.

Second (methyl) acrylate polymer is selected so that first that it can be dissolved in emulsion compositions drop In monomer composition, and make it that it can not be miscible with the first phase.In by drop before the component dissolving of the first monomer composition, Second (methyl) acrylate polymer is formed.Second (methyl) acrylate polymer is conducive to the first of emulsion compositions Stable drop is formed in phase.

Second (methyl) acrylate polymer is generally formed by second comonomer composition.Second comonomer composition is chosen To provide second (methyl) acrylate polymer being dissolvable in water in the first monomer composition.Second comonomer composition and first Monomer composition is differed.In addition, it is often necessary to which second (methyl) acrylate polymer is relatively uniformly distributed throughout emulsion group In all drops in compound.I.e., it is often necessary to the second (methyl) acrylate polymer and pass through the first monomer composition Polymerization formed by polymeric material (that is, first (methyl) acrylate polymer) be both relatively uniformly distributed throughout institute In rewarding polymeric latex particles, even if its composition is differed.First (methyl) acrylate polymer and the second (first Base) acrylate polymer be in identical latex particle within.

Second comonomer composition is selected to provide second (methyl) acrylate polymer, uses differential scanning calorimetry When (for example, modulation system differential calorimetry) is measured, the vitrifying that second (methyl) acrylate polymer has at least 50 DEG C turns Temperature.For example, glass transition temperature is at least 60 DEG C, at least 70 DEG C, at least 80 DEG C, at least 90 DEG C or at least 100 DEG C. Glass transition temperature can be at most 250 DEG C, at most 200 DEG C or at most 175 DEG C.Glass transition temperature is usually from little In 150 DEG C, no more than 140 DEG C, no more than 130 DEG C or no more than 120 DEG C.

Based on the gross weight meter of monomer in second comonomer composition, second comonomer composition generally comprises at least 50 weight % (methyl) acrylate ester, wherein group of naphthene base have at least six carbon atoms.For example, group of naphthene base can have extremely Many 12 carbon atoms, at most 10 carbon atoms or at most 8 carbon atoms.The example of (methyl) acrylate ester monomer includes But it is not limited to：(methyl) isobornyl acrylate, (methyl) acrylic acid 3,3,5- 3-methyl cyclohexanols ester, (methyl) acrylate Ester, (methyl) acrylic acid Buddha's warrior attendant alkyl ester, (methyl) acrylic acid 3,5- dimethyladamantanes ester and the tertiary fourths of (methyl) acrylic acid 4- Base cyclohexyl.

In many embodiments, when being polymerized to homopolymer, (methyl) acrylate ester has at least 80 DEG C Glass transition temperature.Suitable monomer includes but is not limited to：(methyl) isobornyl acrylate, methacrylic acid 3,3,5- tri- Methyl cyclohexyl, cyclohexyl methacrylate, acrylic acid 3,5- dimethyladamantanes base ester and the methacrylic acid 4- tert-butyl groups Cyclohexyl.

(methyl) acrylate ester can be unique monomer in second comonomer composition, or it can be with other Combination of monomers is selected, precondition is：1) when being measured using differential scanning calorimetry (for example, Modulated Differential Scanning Calorimetry), The glass transition temperature of second (methyl) acrylate polymer of gained is equal at least about 50 DEG C；2) second (methyl) obtained by Acrylate polymer is dissolvable in water in the first monomer composition；And 3) second (methyl) acrylate polymer is maintained at breast In the drop of liquid composition, and can not be miscible with the first phase of emulsion compositions.These optional monomers include, for example, polarity Monomer, (methyl) alkyl acrylate with straight or branched alkyl group, (methyl) acrylamide, (methyl) acrylonitrile, N- alkyl (methyl) acrylamide, N, N- dialkyl group (methyl) acrylamide and the second without (methyl) acryloyl group Alkenyl monomer.

Second comonomer composition optionally includes polar monomer, and such as, optional acidiferous monomer is (that is, with acidic groups The monomer of group) or optional hydroxyl monomer (that is, the monomer with oh group).Suitable optionally acidiferous monomer include but It is not limited to：(methyl) acrylic acid, itaconic acid, maleic acid, 2- carboxyethyl acrylates, crotonic acid, citraconic acid, maleic acid, horse Come acid anhydrides (it is hydrolyzed with two hydroxy-acid groups), oleic acid and mono succinate -2- acryloyloxyethyl esters.It is suitable to appoint Hydroxyl monomer is selected to include but is not limited to：Hydroxyalkyl (methyl) acrylate is (for example, (methyl) acrylic acid 2- hydroxyl ethyl esters, (first Base) acrylic acid 2- hydroxypropyl acrylates, (methyl) acrylic acid 3- hydroxypropyl acrylates and (methyl) acrylic acid 4- hydroxy butyl esters) or hydroxyalkyl (first Base) acrylamide (for example, 2- ethoxys (methyl) acrylamide or 3- hydroxypropyls (methyl) acrylamide).Implement many In scheme, optional polar monomer has (methyl) acryloyl group.In many embodiments, optional polar monomer is (first Base) acrylic acid.Second comonomer composition generally comprises 0 weight % to 10 weight %, 1 weight % to 10 weight %, 0 weight % extremely 5 weight % or 1 weight % to 5 weight % optional acidiferous monomer and/or optional hydroxyl monomer.Weight % values are based on second The gross weight meter of monomer in monomer composition.

Second comonomer composition optionally includes (methyl) alkyl acrylate with straight or branched alkyl group. Exemplary monomer includes：(methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) isopropyl acrylate, (methyl) third Olefin(e) acid isobutyl ester, (methyl) n-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) acrylic acid n-pentyl ester, (methyl) third Olefin(e) acid isopentyl ester, (methyl) acrylic acid 2- methylbutyl butenoates, (methyl) the just own ester of acrylic acid, (methyl) acrylic acid 4- methyl -2- penta Ester, the own ester of (methyl) acrylic acid 2- methyl, (methyl) 2-EHA, (methyl) Isooctyl acrylate monomer, (methyl) third Olefin(e) acid n-octyl, (methyl) acrylic acid 2- monooctyl esters, the different nonyl ester of (methyl) acrylic acid, (methyl) isoamyl acrylate, (methyl) third The positive last of the ten Heavenly stems ester of olefin(e) acid, (methyl) isodecyl acrylate, (methyl) acrylic acid 2- Propylheptyls, the different tridecane ester of (methyl) acrylic acid, And (methyl) lauryl ester.The amount of alkyl methacrylate is frequently subjected to second required (methyl) acrylate The limitation of the glass transition temperature of polymer.

Optional monomers other compositions suitable for second comonomer include：(methyl) acrylamide；(methyl) acrylonitrile； N- alkyl (the first of alkyl group with 1 to 10 carbon atom of band (for example, 2 to 10 carbon atoms or 4 to 10 carbon atoms) Base) acrylamide, such as N- octyl acrylamides, NIPA or N tert butyl acrylamide；Or with band 1 To the N of the alkyl group of 10 carbon atoms (for example, 1 to 6 carbon atom or 1 to 4 carbon atom), N- dialkyl group (methyl) third Acrylamide, such as N,N-DMAA.

Other optional monomers may be included in second comonomer composition, and precondition is second (methyl) propylene of gained There is suitable compatibility between the first monomer composition in acid ester polymer and emulsion compositions, and precondition is the Two (methyl) acrylate polymers are dissolvable in water in the drop of emulsion compositions.The example of other optional monomers includes various second Alkenyl monomer, wherein vinyl groups are not (methyl) acryloyl groups.Optional vinyl monomer includes, for example, vinyl acetate Such as vinyl butyrate and various vinyl non-aromatic heterocyclic monomers, such as NVP and N- vinyl Caprolactam.

Cross-linking monomer is not typically included in second comonomer composition.(methyl) acrylate polymer of crosslinking will be difficult to It is dissolved in the first monomer composition.In many embodiments, second comonomer composition does not include aromatic monomer and (that is, had The monomer of aromatic group, such as styrene monomer or aryl (methyl) acrylate).

In many embodiments, second comonomer composition includes 50 weight % to 100 weight % (methyl) acrylic acid Cycloalkanes ester and 0% to 50% optional monomers, such as monomer in following item：Polar monomer, with straight chain or branch (methyl) alkyl acrylate of alkyl group and the vinyl monomer without (methyl) acryloyl group, (methyl) propylene Acid amides, (methyl) acrylonitrile, N- alkyl (methyl) acrylamide, N, N- dialkyl group (methyl) acrylamide and their mixing Thing.For example, second comonomer composition may include 60 weight % to 100 weight % (methyl) acrylate ester and 0 weight Measure % to 40 weight % optional monomers, 70 weight % to 100 weight % (methyl) acrylate ester and 0 weight % extremely 30 weight % optional monomers, 80 weight % to 100 weight % (methyl) acrylate ester and 0 weight % to 20 weights % optional monomers, 90 weight % to 100 weight % (methyl) acrylate ester and 0 weight % are measured to 10 weight %'s Optional monomers, 90 weight % to 99 weight % (methyl) acrylate ester and 1 weight % to 10 weight % optional list Body, 95 weight % to 100 weight % (methyl) acrylate ester and 0 weight % to 5 weight % optional monomers or 95 Weight % to 99 weight % (methyl) acrylate ester and 1 weight % to 5 weight % optional monomers.Weight % is based on The gross weight meter of monomer in second comonomer composition.

In some more particular embodiments, second comonomer composition includes 1) 50 weight % to 100 weight % (first Base) acrylate ester；2) 0 weight % to 50 weight % second comonomer, the second comonomer, which is selected from, has straight or branched alkane (methyl) alkyl acrylate of base group and the vinyl monomer without (methyl) acryloyl group, (methyl) acryloyl Amine, (methyl) acrylonitrile, N- alkyl (methyl) acrylamide and N, N- dialkyl group (methyl) acrylamide；And 3) 0 weight % To 10 weight % polar monomer.For example, second comonomer composition is included：1) 50 weight % to 99 weight % (methyl) propylene Sour cycloalkanes ester, 2) 0 weight % to 50 weight % second comonomer and 3) 1 weight % to 10 weight % polar monomer；Or 1) 50 Weight % to 99 weight % (methyl) acrylate ester, 2) 0 weight % to 40 weight % second comonomer and 3) 1 weight Measure % to 10 weight % polar monomer；Or 1) 70 weight % to 99 weight % (methyl) acrylate ester, 2) 0 weight % To 20 weight % second comonomer and 3) 1 weight % to 10 weight % polar monomer.

In some specific embodiments, second comonomer composition includes 90 weight % to 99 weight % (methyl) propylene Sour cycloalkanes ester and 1% to 10% polar monomer, 95 weight % to 100 weight % (methyl) acrylate ester and (methyl) the acrylate ester and 1% to 5% polarity of 0% to 5% polar monomer or 95 weight % to 99 weight % Monomer.Gross weight meters of the weight % based on monomer in second comonomer composition.In many embodiments, polar monomer is containing acid Monomer, such as, (methyl) acrylic acid.

In addition to second comonomer composition, the polymerisable compound for forming second (methyl) acrylate polymer Usually include chain-transferring agent.Chain-transferring agent is used for the molecular weight for controlling second (methyl) acrylate polymer.Available chain turns The example for moving agent includes but is not limited to：Carbon tetrabromide, alcohol (for example, ethanol and isopropanol), mercaptan are (for example, lauryl mercaptan, fourth Mercaptan, ethyl mercaptan, isooctyl thioglycolate, thioglycollic acid-2-ethyl hexyl ester, mercaptopropionic acid -2- ethylhexyls, double TGAs Glycol ester) and their mixture.In many embodiments, chain-transferring agent preferably is isooctyl thioglycolate (IOTG), carbon tetrabromide, tert-dodecylmercaotan (TDDM) or n-dodecyl mercaptan.Based on single in second comonomer composition The gross weight meter of body, the amount of optional chain-transferring agent is usually in the range of 0 weight % to 5 weight %.If it does, chain tra nsfer Agent is generally used with least 0.01 weight %, at least 0.02 weight %, at least 0.05 weight % or at least 0.1 weight % amount. The amount can be at most 5 weight %, at most 3 weight %, at most 2 weight %, at most 1 weight % or at most 0.5 weight %.

Other optional components can be added to together with second comonomer composition for forming second (methyl) acrylic acid In the polymerisable compound of ester polymer.For example, polymerisable compound can include inhibitor and/or antioxidant.Suitable suppression Preparation and/or antioxidant include but is not limited to：Hydroquinones monomethyl ether (MEQH) and pentaerythrite four (3- (3,5- bis-- The tert-butyl group -4- hydroxyphenyls) propionic ester), it is with trade name IRGANOX 1010 from the bar of New Jersey not Lip river Farnham Parker Si Fu companies (BASF, Florham Park, NJ, USA) are commercially available.

For formed second (methyl) acrylate polymer polymerisable compound generally comprise radical initiator with Monomer is set to start polymerization.Radical initiator can be light trigger or thermal initiator.Based on monomer in second comonomer composition Gross weight meter, radical initiator generally exists with most 5 weight % amount.In some embodiments, radical initiator Amount be at most 4 weight %, at most 3 weight %, at most 2 weight % or at most 1 weight %.Included in polymerisable compound The amount of radical initiator be generally at least 0.005 weight %.For example, polymerisable compound usually includes at least 0.01 weight Measure %, at least 0.02 weight %, at least 0.05 weight %, at least 0.1 weight %, at least 0.2 weight % or at least 0.5 weight Measure % radical initiator.

Suitable thermal initiator includes：Various azo-compounds, such as with trade name VAZO from Delaware, USA Weir The commercially available azo compounds of the E.I.Du Pont Company (E.I.DuPont de Nemours Co., Wilmington, DE, USA) of bright Thing, including VAZO 67 (it is 2,2 '-azo double (2- methylbutyronitriles)), VAZO 64 (it is 2, and 2 '-azo is double (isobutyronitrile)), (it is double (the hexamethylene first of 1,1 '-azo by VAZO52 (it is that 2,2 '-azo is double (2,4- methyl pentane nitriles)) and VAZO 88 Nitrile))；Various peroxide, such as benzoyl peroxide, cyclohexane peroxide, lauroyl peroxide, two-uncle Amyl peroxide, t-butylperoxybenzoate, two-cumyl peroxide and with trade name LUPERSOL (for example, (it is 2,5- bis- by LUPERSOL101 (it is 2,5-bis(t-butylperoxy)-2,5-dimethylhexane) and LUPERSOL 130 Methyl -2,5- two-(t-butylperoxy) -3- hexins)) from the chemical company of Atofina of Philadelphia, PA, USA (Atofina Chemical, Inc., Philadelphia, PA, USA) commercially available peroxide；Various hydroperoxides, Such as t-amyl hydroperoxide and tert-butyl hydroperoxide；And their mixture.

In some embodiments, using light trigger.Some exemplary photo-initiators are benzoin ether (for example, resting in peace Fragrant methyl ether or benzoin isopropyl ether) or substitution benzoin ether (for example, anisoin methyl ether).Other examples light trigger is Substituted acetophenone, such as 2,2- diethoxy acetophenones or 2,2- dimethoxy -2- phenyl acetophenones are (with trade name IRGACURE 651 from New Jersey not Lip river Farnham Parker BASF AG (BASF Corp., Florham Park, NJ, USA) or with trade name ESACURE KB-1 from the Sartomer of Pennsylvania, America Exton (Sartomer, Exton, PA, USA) commercially available).Other other examples light trigger is α -one alcohol (such as 2- methyl -2- hydroxyls of substitution Base propiophenone), aromatics sulfonic acid chloride (such as 2- naphthalene sulfonyl chlorides) and photolytic activity oxime (such as 1- phenyl -1,2- propanedione -2- (O- second Epoxide carbonyl) oxime).Other suitable light triggers are included for example：1- hydroxycyclohexylphenylketones (can be with trade name IRGACURE 184 is commercially available), double (2,4,6- trimethylbenzoyls) phenyl phosphine oxides (can be to be obtained commercially available from trade name IRGACURE 819 ), 1- [4- (2- hydroxyl-oxethyls)-phenyl] -2- hydroxy-2-methyl -1- propane -1- ketone (can be with trade name IRGACURE 2959 is commercially available), 2- benzyl -2- dimethylaminos -1- (4- morpholino phenyls) butanone (can be with trade name IRGACURE 369 It is commercially available), 2- methyl isophthalic acids-[4- (methyl mercapto) phenyl] -2- morpholinyl propyl- 1- ketone (can be with the business of trade name IRGACURE 907 Purchase is obtained) and 2- hydroxy-2-methyl -1- phenyl propyl- 1- ketone (can be with trade name DAROCUR 1173 from New York, United States tower In honest vapour bar special product chemical company (Ciba Specialty Chemicals Corp., Tarrytown, NY, USA) business Purchase is obtained).

In addition, controlling to be used for the glutinous of the polymerisable compound of second (methyl) acrylate polymer of formation if desired Degree, then can add organic solvent.If any, the amount of organic solvent is generally determined by polymerization.It is based at some In the polymerization of solvent, polymerisable compound may comprise up to 70 weight % organic solvent.However, for adiabatic polymerisation side For method, the amount of organic solvent is typically no more than 10 weight % of polymerisable compound, is not more than 8 weight %, is not more than 5 weights Measure %, be not more than 3 weight % or no more than 1 weight %.Any organic solvent used is generally in polymerization in polymerisable compound Reaction is removed after completing.Suitable organic solvent includes but is not limited to：Methanol, tetrahydrofuran, ethanol, isopropanol, heptane, third Ketone, methyl ethyl ketone, methyl acetic acid ester, ethylhexoate, toluene, dimethylbenzene and ethylene glycol alkyl ether.Can be individually or as Its mixture uses these solvents.In many embodiments (such as during some adiabatic polymerisations), exist seldom or It polymerize in the case of in the absence of organic solvent.

Any suitable method can be used to be polymerize for monomer for forming second (methyl) acrylate polymer, such as For example, solution (that is, with solvent) polymerization, dispersin polymerization, suspension polymerisation and solvent-free polymeric with UV or thermal initiator (for example, entered Row polymerisation in bulk).Polymerization can occur in single step or multiple steps.I.e., it is possible to by all or part of polymerisable compound Add in suitable reaction vessel, and be allowed to polymerize.If using multiple steps, the monomer being initially added and initiator added Into reactor.After the material polymerization being initially added, any residual monomer and/or initiator of another part are added.It is multiple Polymerization procedure can aid in the polydispersity (for example, can reduce the amount of low molecular weight chain) for reducing polymerizate, can help Pair tune that can be obtained the type of monomer and measure during making heat of reaction minimum or controlling heat of reaction, and can allow to polymerize It is whole.

In many embodiments, second (methyl) acrylate polymer is not to use emulsion or dispersion polymerization processes Formed.On the contrary, second (methyl) acrylate polymer is prepared using solvent-free bulk polymerization or solution polymerization process. Thermal initiator or light trigger can be used.In some embodiments, polymerization is occurred using adiabatic process, e.g., for example, the U.S. Described in patent 5,986,011 (Ellis et al.) and 5,637,646 (Ellis).This process uses thermal initiator.

The weight average molecular weight of second (methyl) acrylate polymer is generally at least 3,000 grams/mol.If divided equally again Son amount is lower, then the cohesive strength of gained contact adhesive low may be obtained and can not received.Second (methyl) acrylate polymer Usually from least 5,000 grams/mol, at least 10,000 grams/mol or at least 20,000 grams/mol of weight average molecular weight.Weight is equal Molecular weight can be up to 150,000 grams/mol.If molecular weight is higher, second (methyl) acrylate polymer may nothing Method is dissolved in the first monomer composition of emulsion compositions.If can not be dissolved in the first monomer composition, the second (first Base) acrylate polymer can undesirably be present in the drop separated with the first monomer composition in emulsion compositions In, and/or may be separated during polymerizeing.Weight average molecular weight usually be at most 120,000 grams/mol, at most 100,000 grams/mol, at most 80,000 grams/mol, at most 60,000 grams/mol or at most 50,000 grams/mol.For example, Weight average molecular weight can be in the range of 3,000 grams/mol to 150,000 grams/mol, at 10,000 grams/mol to 150,000 To 100 in the range of gram/mol, in the range of 3,000 grams/mol to 100,000 grams/mol, at 10,000 grams/mol, In the range of 000 gram/mol, in the range of 3,000 grams/mol to 50,000 grams/mol or at 10,000 grams/mol extremely In the range of 50,000 grams/mol.

Second (methyl) acrylate polymer is added in emulsion compositions.That is, other with emulsion compositions Before component merges, the polymeric material is prepared.Second (methyl) acrylate polymer is not generally within emulsion compositions Or radical polymerization does not occur further for other components with emulsion compositions.However, second (methyl) acrylate can be Reaction is crosslinked within emulsion compositions.

Second (methyl) acrylate polymer is generally added to Emulsion combination after the first monomer composition is dissolved in In thing.That is, the solution comprising second (methyl) acrylate polymer is added to the of emulsion together with the first monomer composition In one phase.The solution is generally added under high shear mixing conditions, to form the drop being suspended in the first phase.In some implementations In scheme, second (methyl) acrylate polymer is initially dissolved in a part of first monomer composition, then again by gained Polymer solution mixed with the residual monomer of the first monomer composition.

The amount of second (methyl) acrylate polymer being added in emulsion compositions be generally at least 0.5 weight %, Or at least 1 weight %.If with the addition of lesser amount of second (methyl) acrylate polymer, the stability of emulsion compositions May be worse.That is, it is likely difficult to that drop is formed and remained in emulsion compositions.In some embodiments, emulsion group Compound includes at least 2 weight %, at least 3 weight % or at least 5 weight % second (methyl) acrylate polymer.Second The addition of (methyl) acrylate polymer is generally at most 15 weight %.If with the addition of the second (methyl) third of higher amount Olefine acid ester polymer, then polymerization of first monomer composition in drop low may be obtained and can not received.In addition, by the first monomer group The polymeric material of compound formation may have undesirable low molecule amount, and gained contact adhesive may be with undesirable Low cohesive strength.In some embodiments, emulsion compositions include at most 12 weight %, at most 10 weight % or at most 8 Weight % second (methyl) acrylate polymer.Gross weights of the weight % based on the first monomer composition in emulsion compositions (that is, the gross weight of monomer in the first monomer composition) is counted.

Emulsion compositions include the first monomer composition and second (methyl) acrylate polymer in same droplet Both.More particularly, the gross weight based on second (methyl) acrylate polymer and monomer in the first monomer composition Weight sum (this does not include a small amount of polymerisable surfactant) meter, emulsion compositions usually include 0.5 weight % to 15 weights Measure % the second (methyl) acrylate polymer and 85 weight % to 99.5 weight % the first monomer composition.This is breast Polymerization and the summation of polymerizable material in liquid composition.Most of the polymerization and polymerizable material are present within emulsion droplet (for example, some acid monomer-soluble solutions are in first phase).In some instances, based on second (methyl) acrylate polymer Gross weight and the first monomer composition in monomer weight sum meter, emulsion compositions can include：1 weight % to 15 weight % The second (methyl) acrylate polymer and 85 weight % to 99 weight % the first monomer composition, 2 weight % to 12 Weight % the second (methyl) acrylate polymer and 88 weight % is to 98 weight % the first monomer composition, 2 weights Measure % to 10 weight % the second (methyl) acrylate polymer and 90 weight % to 98 weight % the first combination of monomers Thing, or 2 weight % to 8 weight % the second (methyl) acrylate polymer and 92 weight % to the first of 98 weight % Monomer composition.

In some specific embodiments, the first monomer composition includes the mixture of following item：With band at least six One or more (methyl) alkyl acrylate, one or more (methyl) propylene of the straight or branched alkyl group of carbon atom Sour cycloalkanes ester or one or more (methyl) acrylic acid.Second (methyl) acrylate is by including one or more (methyl) third The second comonomer composition of olefin(e) acid cycloalkanes ester and one or more (methyl) acrylic acid is formed.

Other optional reactants can be included in emulsion compositions.For example, in some embodiments, crosslinking agent is added, The crosslinking agent can react with a variety of hydroxy-acid groups (- COOH).Hydroxy-acid group can on second (methyl) acrylate polymer, On the polymeric material that the first monomer composition is formed or in the combination of both polymeric materials.Use optional crosslinking agent The shear strength of gained contact adhesive can be increased.

The suitable crosslinking agents that can be reacted with a variety of hydroxy-acid groups include but is not limited to：Polyoxazoline, such as can be with commodity EPOCROS is from Nippon Shokubai Co., Ltd (Nippon Shokubai Co., LTD, Japan) commercially available polyoxazolines for name； Polyaziridine (for example, derived from New Jersey De Fude PolyAziridine companies (PolyAziridine LCC, Medford, NJ, USA) trimethylolpropane-three (2- methyl isophthalic acids-ethylene imine) propionic ester)；Polyamine etc..Other suitable friendships Join the metal salt that agent includes to be complexed with multiple hydroxy-acid groups.Suitable metal includes, for example, zinc salt.If you are using, Based on the gross weight meter of monomer in the first monomer composition, the addition of optional crosslinking agent is usually equal at least about 0.01 weight %. For example, emulsion can include at least 0.05 weight %, at least 0.1 weight % or at least 0.5 weight % crosslinking agent.Based on first The gross weight meter of monomer in monomer composition, the amount of optional crosslinking agent is at most usually 3 weight %.For example, emulsion compositions can Include at most 2.5 weight %, at most 2 weight %, at most 1.5 weight % or at most 1 weight % optional crosslinking agent.

In many embodiments, optional nertralizer is added in emulsion compositions.Nertralizer can be added, for example, with The reactivity of crosslinking agent is improved, stability to improve gained latex composition etc..Suitable nertralizer usually from highly basic or weak Alkali, such as, ammonium hydroxide, ammonia, sodium acetate, potassium acetate, sodium hydroxide, potassium hydroxide and lithium hydroxide.Generally add nertralizer So that the pH of emulsion compositions is increased at least 4.0, at least 4.5, at least 5.0, at least 5.5, at least 6.0, at least 6.5 or extremely Few 7.0.

Emulsion compositions generally also include initiator.Although water-soluble or oil-soluble initiator can be used, generally Initiator during selection is water-soluble.If initiator is oil-soluble, the first monomer composition is generally added to In the mixture (solution) of monomer and second (methyl) acrylate polymer, the mixture (solution) and emulsion are then remixed First phase of composition.It is usually right after formation drop in the first phase of emulsion compositions if initiator is water solubility It is added.If having used reducing agent, it typically is water solubility, and it is added in the first phase.

The example of water soluble starter includes but is not limited to：Hydrogen peroxide and various persulfates, such as sodium peroxydisulfate, mistake Potassium sulfate and ammonium persulfate.Optional reducing agent can be added to reduce the temperature needed for initiated polymerization.Suitable reducing agent Including but not limited to：Ascorbic acid, bisulfites (for example, sodium hydrogensulfite, potassium bisulfite and ammonium bisulfite) and Rongalite.Based on the weight meter of monomer in the first monomer composition, the amount of initiator and optional reducing agent can be At most 1 weight %.For example, the gross weight meter based on monomer in the first monomer composition, the amount can be at most 0.8 weight %, At most 0.5 weight %, at most 0.3 weight % or at most 0.2 weight %.Gross weight based on monomer in the first monomer composition The amount of meter, initiator and optional reducing agent can be at least 0.01 weight %, at least 0.05 weight % or at least 0.1 weight %.

The example of oil-soluble initiator includes but is not limited to：Azo-compound or peroxide, it is all as described for formation Those of second (methyl) acrylate polymer.If using such initiator, with identical with above-mentioned water soluble starter Amount use such initiator.

In many emulsion compositions, without using chain-transferring agent.However, as set forth above, it is possible to inciting somebody to action (and generally inciting somebody to action) chain Transfer agent is used to form second (methyl) acrylate polymer.

Emulsion compositions do not include tackifier.

Emulsion compositions can be prepared by any suitable process：The process is resulted in comprising second (methyl) acrylic acid The drop of ester polymer, second (methyl) acrylate polymer is dissolved in the monomer of the first monomer composition.In many realities Apply in scheme, second (methyl) acrylate polymer is initially mixed with the monomer included in the first monomer composition.It is described Monomer is usually used in the case of without adding any solvent with its simple form.Once second (methyl) acrylate Polymer has dissolved, then using high shear mixing combine the mixture (solution) and water or with water and emulsion compositions Other components.In some embodiments, polymerisable surfactant and nertralizer can be dissolved in the water before mixing (or Combined with water).

By high shear mixing, droplet formation is within the first phase (that is, aqueous phase).In any poly- of the first monomer composition Before conjunction, drop includes the mixture with following item：I) second (methyl) acrylate polymer；And ii) at least 90 weights % the first monomer composition is measured, wherein second (methyl) acrylate polymer is dissolved in the first monomer composition in drop In.Drop generally comprises at least 92 weight %, at least 95 weight %, at least 97 weight %, at least 98 weight % or at least 99 weights Measure the monomer in % the first monomer composition.Polymerisable surfactant is most likely in the interface between drop and the first phase Place is dissolved in the first phase.Most of polymerisable surfactants are most likely in interface.In many embodiments, it is newborn Any initiator, and/or reducing agent, and/or nertralizer included in liquid composition are likely to be dissolved in the first phase.

The average diameter for the drop being suspended in the first phase is usually at most about 2000 nanometers, at most 1500 nanometers, at most 1000 nanometers, at most 900 nanometers, at most 800 nanometers, at most 700 nanometers, at most 600 nanometers or at most 500 nanometers.It is average straight Footpath is generally at least 100 nanometers, at least 200 nanometers, at least 300 nanometers or at least 400 nanometers.Dynamic can be used in average-size Light scattering determining.In some embodiments, mean droplet size (diameter) is in 100 nanometers to 2000 nanometer ranges, 200 Nanometer is in 1000 nanometer ranges, in 300 nanometers to 1000 nanometer ranges, in 200 nanometers to 800 nanometer ranges or 400 nanometers To 700 nanometer ranges.

In many embodiments, emulsion compositions are considered as miniemulsion.As used herein, term " miniemulsion " is to instigate The emulsification method that average diameter is not more than 1 micron of drop is prepared with high shear.Polymerization occurs poly- to be formed within drop Close latex particle.Polymerization is limited to：Occur within drop.

Usual (for example, about 20 DEG C to about 25 DEG C) at room temperature or it polymerize the first combination of monomers at a temperature of more than room temperature Thing.Usually from least 30 DEG C, at least 40 DEG C or at least 50 DEG C of temperature.Temperature may be up to the boiling temperature (example of emulsion compositions Such as, about 100 DEG C).In some embodiments, temperature can be at most 80 DEG C, at most 70 DEG C or at most 60 DEG C.During polymerization Any heat produced is promptly acted on by the thermal capacity of the first phase to be relaxed.Reaction time can be complete polymerisation needed for Any duration.In some embodiments, the reaction time can be at least 1 hour, at least 2 hours, at least 3 hours or at least 4 Hour.Reaction time is most 24 hours or longer, most 16 hours or most 8 hours.The reactor usually uses inert gas Such as nitrogen is purged.

The polymerizate of emulsion compositions is latex composition.That is, latex composition includes water and polymer particles, polymerize grain Son is the polymerizate of emulsion compositions as described above.Term " latex " and " latex composition " are used interchangeably.Term is " poly- Conjunction particle " and " latex particle " and " polymeric latex particles " are used interchangeably.Both it is present in identical latex particle below In：I) the second (methyl) acrylate polymer and；Ii) polymerizate (first (methyl) propylene of the first monomer composition Acid ester polymer).Latex composition includes latex particle, and the average-size of the latex particle is equivalent to Emulsion combination before polymerization The average-size of drop in thing.More specifically, due to density variation, the particle mean size of latex particle is substantially equal to or somewhat big In the average-size of drop in emulsion compositions.

Latex particle is typically suspended in (for example, being dispersed in) aqueous phase (the first phase).Preferably, latex particle does not coagulate Knot is together.Latex particle includes the second (methyl) acrylate polymer and first (methyl) acrylate polymer two Person.The molecular weight of first (methyl) acrylate polymer is usually above the Chemical composition that by identical total amount using other processes The molecular weight of the polymeric material of formation.More specifically, first (methyl) acrylate polymer formed by emulsion polymerization Molecular weight can be close to 1 megadalton.

With for form the emulsion polymerization method of first (methyl) acrylate polymer on the contrary, using solution polymerization process or The typical molecular weight for the polymer that mass polymerization is formed by same monomer is usually from less than 500,000 dalton.Pass through solution Both polymerization and mass polymerization, molecular weight are generally controlled by the concentration of initiator.That is, initiator concentration is higher, Often produce the polymer of more small-molecular-weight.Therefore, in order that generating high-molecular-weight poly with solution polymerization process or mass polymerization Compound is, it is necessary to the extremely low initiator of concentration.If however, the extremely low initiator of concentration, polymerization time may grow nothing Method receives.Economically, this class process may be unrealistic for preparing high molecular weight polymer material.However, for one A little adhesive applications, all applications if desired for using high shear strength, it is often necessary to high molecular weight polymer material.

By emulsion polymerization, the molecular weight of polymeric material is (for example, the molecule of first (methyl) acrylate polymer Amount) it can be controlled by both initiator concentration and number of particles (that is, the number of drop in emulsion).Initiator concentration is got over Height, it is smaller to frequently result in molecular weight, and the reaction time is faster.However, number of particles is bigger, often make it that molecular weight is bigger, And the reaction time is faster.

Compared with using solution polymerization process and the polymeric material of mass polymerization formation, due to being formed by emulsion compositions Polymeric material HMW, or even in the case of in the absence of other crosslinking agent, cross-linked structure usually can more be held Change places to be formed.The possible crosslinking of two classes can be betided in the polymeric material formed by emulsion polymerization：1) physical entanglement and 2) chemical crosslinking occurred due to the chain transfer reaction of polymer chain.It can be twined with longer polymer chain to strengthen physics Knot, longer polymer chain is derived from the mean molecule quantity being increased.Chain transfer reaction can be polymeric long chain into crosslinking Structure.

As determined using differential scanning calorimetry (DSC), latex particle generally has single glass transition temperature.More specifically Ground is said, during the second heating cycle carried out using Modulated Differential Scanning Calorimetry, and dry polymer material (dries latex Polymer particles) Reversing heat flow and temperature curve map in exist it is unimodal.Tg is usually more than 0 DEG C, is not more than -10 DEG C or not More than -20 DEG C.

Latex composition can be combined with optional tackifier.Add tackifier and can be used for increase adhesion.It can be used any Suitable tackifier, such as rosin acid and its derivative (for example, rosin ester)；Terpene resin, such as polyterpene are (for example, based on α pinanes The resin of alkene, the resin based on beta pinene and the resin based on limonene) and aromatic modified polyterpene resin (for example, phenol is modified Polyterpene resin)；Coumarone-indene resin；With the hydrocarbon resin based on oil, such as hydrocarbon resin based on C5, the hydrocarbon tree based on C9 Fat, the hydrocarbon resin based on C5/C9 and the resin based on bicyclopentadiene.These tackifying resins (if addition) can be by hydrogen Change to reduce their Color influences to pressure-sensitive adhesive composition.If desired, the combination of various tackifier can be used.

In many embodiments, tackifier are rosin ester or include rosin ester.Rosin ester tackifier is various rosin acids With the reaction product of alcohol.These include but is not limited to：The methyl ester of rosin acid, the triglycol ester of rosin acid, rosin acid it is sweet The pentaerythritol ester of grease and rosin acid.These rosin esters can partially or even wholly be hydrogenated to improve stability and reduce Influence of their color to pressure-sensitive adhesive composition.Rosin resin tackifier can for example with trade name PERMALYN, Eastman Chemical (Eastman Chemicals of the STAYBELITE and FORAL from this golden baud of tennessee,USA Company (Kingsport, TN, USA)) and it is industrial from the Newport of London with trade name NUROZ and NUTAC (Newport Industries (London, England)) is commercially available.Complete all hydrogenated rosin resin can be for example with trade name FORAL AX-E are commercially available from Eastman Chemical (Eastman Chemical Company).Partially hydrogenated rosin tree Fat can be obtained for example with trade name STAYBELITE-E commercially available from Eastman Chemical (Eastman Chemical Company) .

Usually need to use the tackifier being dispersed among in water.The aqueous dispersion of rosin ester can with trade name SNOWTACK from The Lauth OY (Lawter, Inc., Chicago, IL, USA) in Illinois, USA Chicago obtains.Other suitable moisture Dissipating type tackifier can be obtained with trade name TACOLYN commercially available from Eastman Chemical Company (Eastman Chemical Company) , it is included, for example, rosin ester resin dispersion, rosin ester resin dispersion, aliphatic hydrocarbon resin dispersion and the virtue of hydrogenation The hydrocarbon resin dispersion that race is modified.

If it exists, the optional tackifier in the gross weight meter based on emulsion polymerization particle, latex composition are usually Used with the amount in the range of 1 weight % to 40 weight %.In some embodiments, the amount of tackifier be at least 5 weight %, Or at least 10 weight %, and can be at most 35 weight %, at most 30 weight %, at most 25 weight % or at most 20 weights Measure %.

Other optional components being added in latex composition are thickener.Exemplary thickener is usually polymer The aqueous solution, such as imperial coating with trade name PARAGUM from Indiana, USA South Bend and special copolymer company The aqueous solutions of polymers that (Royal Coatings and Specialty Polymers, South Bend, IN, USA) is obtained. If addition, based on the gross weight meter of latex composition (for example, water and polymeric latex particles), optional thickener can be with At most 5 weight % amount is used.For example, thickener can with most 4 weight %, at most 3 weight %, at most 2 weight % or at most 1 weight % amount is used.In some embodiments, thickener is in following scope：0 weight % is to 5 weight %, 0.1 weight Measure % to 5 weight %, 0.1 weight % to 2 weight %, 0.1 weight % to 1 weight %, 0.2 weight % to 0.8 weight % or 0.4 weight % to 0.6 weight %.

Latex composition is generally dried to form contact adhesive.Usual dry compositions are to remove at least 90 weight %'s Water.For example, removing at least 95 weight %, at least 97 weight %, at least 98 weight % or at least 99 weight % water.Dry The water content of contact adhesive can be increased or decreased according to ambient humidity.In some embodiments, before the drying by latex Composition is applied in substrate, on such as back sheet or release liner.Drying generally occurs at a temperature of more than room temperature, without It is to occur at a temperature of substrate and/or pressure sensitive adhesive layer is deformed or is degraded.In some embodiments, dry about 40 DEG C occur, and dry duration to be enough water content being reduced to required level within the temperature range of about 120 DEG C.

Pressure sensitive adhesive layer can have any required thickness.In many embodiments, adhesive phase has no more than 20 (100 is micro- for mil (500 microns), no more than 10 mils (250 microns), no more than 5 mils (125 microns), no more than 4 mils Rice), be not more than the thickness of 3 mils (75 microns) or no more than 2 mils (50 microns).The thickness usually from least 0.5 mil (12.5 microns) or at least 1 mil (25 microns).For example, the thickness of adhesive phase can be in 0.5 mil (2.5 microns) to 20 close In the range of ear (500 microns), in the range of 0.5 mil (5 microns) to 10 mils (250 microns), 0.5 mil (12.5 microns) In the range of to 5 mils (125 microns), in the range of 1 mil (25 microns) to 3 mils (75 microns) or 1 mil (25 microns) To 2 mils (50 microns).

Contact adhesive can have the balance of good peel strength and adhesion strength.There is the second (first in emulsion droplet Base) acrylate polymer can help to form this good balance.Without using the second (methyl) third in emulsion compositions Olefin(e) acid ester, it may be difficult to which preparing has this well balanced contact adhesive.That is, peel strength is keeping good cohesive strength When can be increased.Similarly, cohesive strength interior can increase when keeping good peel strength.

All kinds preparation can be prepared, the product includes substrate and pressure sensitive adhesive layer, and pressure sensitive adhesive layer is neighbouring (simultaneously And adhere to) positioning of the main surface of substrate.Any suitable substrate can be used in product, and substrate is usually according to concrete application Selected.For example, substrate can be flexible or non-flexible, and can be by polymeric material, glass or ceramic material, gold Category or metal alloy or combinations thereof are formed.Some substrates are polymeric material, such as prepared by (such as) following item Polymeric material：Polyolefin (for example, polyethylene, polypropylene or their copolymer), polyurethane, polyvinyl acetate, polychlorostyrene Ethene, polyester (for example, polyethylene terephthalate or PEN), makrolon, polyacrylate (such as poly- (methyl) methyl acrylate (PMMA)), ethylene-vinyl acetate copolymer, neoprene and cellulosic material (for example, cellulose acetate, cellulose triacetate and ethyl cellulose).Substrate can be following form：Paper tinsel, film or piece, non-knit Producing material material (for example, paper wood, fabric, non-woven scrim), foam etc..

For some substrates, it may be necessary to handle the surface of substrate to improve the adhesion with pressure-sensitive adhesive layer.Such place Reason includes, for example, apply prime coat, surface reforming layer (for example, sided corona treatment or surface abrasion), or both.Suitable chemistry The exemplary example of prime coat class includes：Polyurethane, organosilicon, epoxy resin, vinyl acetate resin, aziridine etc..Urine Alkanes and organic silicon are the particularly effective chemical primers being used together with polyester film substrates.The suitable organosilicon priming paint of one class Layer has the inorganic particulate of continuous gel network structure, and is described in Japanese Unexamined Patent announcement (Kokai) 2- In 200476.The prime coat has strong affinity to polyester resin and vistanex.Vinyl and poly terephthalic acid second two The exemplary example of the chemical primers of alcohol ester film includes：Acrylate/acrylic copolymer of crosslinking, it is disclosed in United States Patent (USP) In No.3,578,622 (Brown).

In some embodiments, substrate is release liner.Release liner generally has low affine to pressure sensitive adhesive layer Power.Exemplary release liner can be prepared by paper wood (for example, brown paper) or other types of polymeric material.Some peeling liners Pad is coated with remover outer layer, such as, the material containing organosilicon or the material containing fluorocarbon.

Some products are adhesive tape.Adhesive tape can be single-sided adhesive tape, wherein having on the one side of back sheet pressure-sensitive Adhesive, or can be double-faced adhesive tape, wherein having pressure sensitive adhesive layer on two main surfaces of back sheet.Back sheet Usually from polymer film, fabric or foam.Each pressure sensitive adhesive layer can position (if desired) back sheet and peel ply it Between.

Any suitable back sheet can be used.In some embodiments, back sheet is the polyolefin film of orientation.Example Such as, the polyolefin film of orientation can be prepared as United States Patent (USP) 6,638,637 (Hager et al.) is described.Such back sheet is normal Often include multiple polyolefin layers, what these polyolefin layers had at least two different melting points and were biaxially oriented.In another example In, the polyolefin film of orientation can be prepared as United States Patent (USP) 6,451,425 (Kozulla et al.) is described.Such backing is normal Isotactic polypropylene is often included, isotactic polypropylene is blended or mixed with least one second polyolefin, second polyolefin Such as polyethylene, polybutene or syndiotactic polypropylene.What these backings were generally biaxially oriented.

For the adhesive tape with single pressure sensitive adhesive layer, back sheet usually has by processing (that is, priming) To improve the first surface to the adhesion of pressure sensitive adhesive layer.Back sheet have it is relative with first surface, to contact adhesive Layer has the second surface of low adhesion.Such adhesive tape is formed as volume.In some embodiments, adhesive tape is packaging glue Band.

Other products are transfer belt, and wherein pressure sensitive adhesive layer is positioned adjacent to release liner.Transfer belt can be used for will be pressure-sensitive Adhesive phase is transferred on another substrate or surface.Any suitable release liner can be used.In many embodiments, shell From peel ply coating of the pad with adjacent substrate.Suitable substrate includes but is not limited to：Paper wood, it is such as, polymer-coated Brown paper and supercalendering brown paper or thin glass brown paper；Cloth (fabric)；Nonwoven webs；Metal or metal alloy, bag Include metal foil；Polyester, such as poly- (alkylene terephthalate) (such as poly- (ethylene glycol terephthalate)), poly- (naphthalene diformazan Sour alkylene carbonate) (such as poly- ((ethylene naphthalate)))；Makrolon；Polyolefin, such as polypropylene, polyethylene, polybutene, And their copolymer；Polyamide；Cellulosic material, such as cellulose acetate or ethyl cellulose；And combinations thereof.

In some example embodiments, release liner has barrier coat, and the coating includes such as United States Patent (USP) No.5, The polymerizate of vinyl-Organosiliconcopolymere described in 032,460 (Kantner et al.).In other examples embodiment party In case, release liner has barrier coat, and the coating includes such as U.S. Patent Application Publication No.2013/059105 (Wright People) described in (methyl) acrylate functional siloxanes polymerizate.Such release coating can be prepared by the following procedure：Will The coating of polymerisable compound comprising (methyl) acrylate functional polysiloxanes is applied to the surface of substrate, then with purple UV radiation irradiates coating.Ultraviolet radiation is usually provided by polychrome short wavelength UV line source, the polychrome short wave ultraviolet Light source has at least one peak value, and its density is in about 160 nanometers to about 240 nanometers of wave-length coverage.Suitable polychrome is short Ripple ultraviolet light source includes, for example, low pressure mercury vapor lamp, low pressure mercury alloy lamp, pulsed xenon lamp and from illuminated plasma The glow discharge of body emission source.Gross weight meter based on coating, the coating for being applied to substrate can be free of or substantially free of (example Such as, less than 0.1 weight %, less than 0.01 weight % or less than 0.001 weight %) light trigger.

Pressure sensitive adhesive layer usually has high peel adhesion (that is, peel strength), and high shear strength (that is, cohesion Power) so that surface is smooth and coarse.In this way, contact adhesive can be used in the various product of purposes, and it can be adhered a variety of Substrate.In some embodiments, substrate is polymer film or piece, metal or metal alloy, fabric or foam.

In the embodiment wherein without using tackifier or using a small amount of tackifier, contact adhesive is very suitable for needing In the application for wanting a small amount of volatile organic content, such as, automotive trim application.Contact adhesive usually has high peel adhesion With high shear strength (that is, cohesive force), when especially adhering to low-surface-energy substrate, such as polyolefin is (for example, polypropylene, poly- Ethene, polybutene and their copolymer) and clear coat.At a temperature of more than the room temperature, such as close to that of 70 DEG C At a little temperature, good adhesive properties (for example, high peel adhesion and high shear strength) can be generally also kept.

In the embodiment of tackifier is wherein included, contact adhesive usually has high peel adhesion and high shear strong Degree, when especially adhering on polar surfaces, such as metal or metal alloy (for example, carbon steel and stainless steel).

Embodiment 1 is a kind of emulsion compositions, comprising：A) water, the insatiable hunger of Raolical polymerizable can be carried out by b) having With the polymerisable surfactant of group, c) the first monomer composition, and d) second (methyl) acrylate polymer.First Monomer composition includes (methyl) alkyl acrylate that straight or branched alkyl group has at least six carbon atoms.Based on first The total monomer weight of monomer composition, the second (methyl) acrylate polymer is deposited with 0.5 weight % to 15 weight % amount , and its glass transition temperature is more than or equal to 50 DEG C.Second (methyl) acrylate polymer is combined by second comonomer Thing is formed, and based on the gross weight meter of monomer in second comonomer composition, the second comonomer composition includes at least 50 weight %'s (methyl) acrylate ester, wherein group of naphthene base have at least six carbon atoms.Emulsion compositions include the first phase and the Two-phase, first mutually include water, and second as droplet distribution in the first phase.Drop includes the mixture of following item：i) At least 90 weight % the first monomer composition；And ii) second (methyl) acrylate polymer.Second (methyl) acrylic acid Ester polymer can not be miscible with the first phase, and in the first monomer composition being dissolved in drop.

Embodiment 2 is the emulsion compositions according to embodiment 1, wherein when being measured as homopolymer, second (methyl) acrylate ester has the glass transition temperature equal at least about 80 DEG C in monomer composition.

Embodiment 3 is the emulsion compositions according to embodiment 1 or 2, wherein the first monomer composition is also included (methyl) acrylate ester, polar monomer, or both.

Embodiment 4 is the emulsion compositions according to any one of embodiment 1 to embodiment 3, wherein being based on The gross weight meter of monomer in first monomer composition, the first monomer composition includes 60 weight % to 98 weight % straight or brancheds Alkyl group has (methyl) alkyl acrylate of at least six carbon atoms, 1 weight % to 30 weight % (methyl) acrylic acid The polar monomer of cycloalkanes ester and 1 weight % to 10 weight %.

Embodiment 5 is the emulsion compositions according to any one of embodiment 1 to 4, wherein based on second comonomer The gross weight meter of monomer in composition, second comonomer composition includes 50 weight % to 100 weight % (methyl) acrylic acid ring The optional monomers of alkyl ester and 0 weight % to 50 weight %, the optional monomers are polar monomer, with straight or branched alkyl (methyl) alkyl acrylate of group, the vinyl monomer without (methyl) acryloyl group, (methyl) acrylamide, (methyl) acrylonitrile, N- alkyl (methyl) acrylamide, N, N- dialkyl group (methyl) acrylamide or their mixture.

Embodiment 6 is the emulsion compositions according to any one of embodiment 1 to embodiment 5, wherein being based on The gross weight meter of monomer in second comonomer mixture, second comonomer composition includes 90 weight % to 99 weight % (methyl) third (methyl) acrylate ester of olefin(e) acid cycloalkanes ester and 1% to 10% polar monomer or 90 weight % to 100 weight % And 0 weight % to 10 weight % polar monomer.

Embodiment 7 is the emulsion compositions according to any one of embodiment 1 to 6, wherein the first combination of monomers Thing is different from second comonomer composition.

Embodiment 8 is the emulsion compositions according to any one of embodiment 1 to embodiment 7, wherein second The weight average molecular weight of (methyl) acrylate polymer is in the range of 3,000 grams/mol to 150,000 grams/mol.

Embodiment 9 is the emulsion compositions according to any one of embodiment 1 to embodiment 8, wherein emulsion Composition does not include tackifier.

Embodiment 10 is the emulsion compositions according to any one of embodiment 1 to 9, wherein based on Emulsion combination The gross weight meter of thing, emulsion compositions include at least 25 weight % water.

Embodiment 11 is the emulsion compositions according to any one of embodiment 1 to 10, wherein based on emulsion group The gross weight meter of compound, emulsion compositions include at most 90 weight % water.

Embodiment 12 is the emulsion compositions according to any one of embodiment 1 to 11, wherein polymerizable surface Activating agent is acrylic polyoxyethylene alkylphenyl compound or acrylic polyoxyethylene alkyl phenyl ether ammonium sulfate compound.

Embodiment 13 is the emulsion compositions according to any one of embodiment 1 to 12, wherein polymerizable surface Activating agent is Sodium Dodecyl Allyl Sulfosuccinate or phosphate.

Embodiment 14 is the emulsion compositions according to any one of embodiment 1 to 13, wherein single based on first The gross weight meter of monomer in body composition, emulsion compositions include at least 0.5 weight % polymerisable surfactant.

Embodiment 15 is the emulsion compositions according to any one of embodiment 1 to 14, wherein single based on first The gross weight meter of monomer in body composition, emulsion compositions include at most 2 weight % polymerisable surfactant.

Embodiment 16 is comprising the poly- of the emulsion compositions according to any one of embodiment 1 to embodiment 15 The latex composition of product is closed, wherein latex composition includes emulsion polymerization particle.

Embodiment 17 is the latex composition according to embodiment 16, wherein as used differential scanning calorimetry (DSC) institute Determine, emulsion polymerization particle has single glass transition temperature.

Embodiment 18 is the latex composition according to embodiment 16 or embodiment 17, wherein second (methyl) The polymerizate of acrylate polymer and the first monomer composition is in identical polymer particles together.

Embodiment 19 is the latex composition according to any one of embodiment 16 to embodiment 18, is also included Water-dispersion type tackifier.

Embodiment 20 is the latex composition according to any one of embodiment 16 to embodiment 19, wherein base In the gross weight meter of emulsion polymerization particle, the polymerizate of emulsion compositions is included in the amount in the range of 1 weight % to 2 weight % Polymeric surfactant.

Embodiment 21 is comprising the latex composition according to any one of embodiment 16 to embodiment 20 The contact adhesive of desciccate.

Embodiment 22 is a kind of product, and it includes the first of the first main surface positioning of (a) substrate and (b) adjacent substrate Pressure sensitive adhesive layer, wherein the first pressure sensitive adhesive layer includes the contact adhesive according to embodiment 21.

Embodiment 23 is the product according to embodiment 22, includes the second main surface positioning of adjacent substrate The second layer of the contact adhesive of embodiment 21.

Embodiment 24 is the product according to embodiment 22 or embodiment 23, and wherein substrate is foam or polymerization Thing film.

Embodiment 25 is the product according to any one of embodiment 22 to embodiment 24, and wherein substrate is double The polyolefin film of axle orientation.

Embodiment 26 is the product according to any one of embodiment 22 to embodiment 24, wherein substrate be every From liner.

Embodiment 27 is the product according to embodiment 26, and wherein release liner includes barrier coat, and isolation is applied Polymerizate of the layer comprising vinyl-Organosiliconcopolymere or (methyl) acrylate-Functionalized siloxanes.

Embodiment 28 is the product according to embodiment 26 or embodiment 27, and wherein product is transfer belt.

Embodiment 29 is the product according to embodiment 22 to embodiment 25, and wherein product is adhesive glue Band.

Embodiment 30 is the product according to embodiment 29, and wherein adhesive tape is gummed tape.

Embodiment 31 is the product according to any one of embodiment 22 to embodiment 25, and wherein substrate has Low-energy surface.

Embodiment 32 is the product according to embodiment 31, and wherein low-energy surface includes polyolefin or transparent painting Layer.

Embodiment 33 is a kind of method for forming contact adhesive.This method includes：(a) formed according to embodiment 1 To the emulsion compositions any one of embodiment 15；(b) emulsion compositions polymerization is made to include emulsion polymerization grain to be formed The latex composition of son；And (c) dries latex composition to form contact adhesive.

Embodiment 34 is the method according to embodiment 33, wherein forming emulsion compositions includes：Form second (methyl) acrylate polymer；By second (methyl) acrylate polymer be dissolved in one kind in the first monomer composition or To form polymer solution in various of monomer；Polymer solution is added in the first phase；And by high shear mixing The drop of polymer solution is formed in one phase.

Embodiment：

Except as otherwise noted, otherwise number, percentage, ratio all in embodiment etc. is by weight.

As used herein, term " pph " refers to the number in every 100 parts.

Table 1：Material

Method of testing 1：The measurement of polymer molecular weight

The molecular weight distribution of compound is characterized using gel permeation chromatography (GPC).GPC instruments are purchased from U.S. horse The water generation company (Waters Corporation, Milford, MA, USA) of Sa Zhusai states Penelope Milford, it includes high pressure liquid Phase chromatogram pump (model 1515HPLC), automatic sampler (model 717), UV detectors (model 2487) and refractive index detector (model 2410).The chromatograph is furnished with two Varian Inc. (Varian from California, USA Paro Otto Inc. (Palo Alto, CA, USA)) the 5 microns of PLgel MIXED-D chromatographic columns obtained.

The preparation method of polymer solution sample is：By dry polymer samples with the concentration of 0.5% (weight/volume) It is dissolved in tetrahydrofuran, and solution is filtered through to the VWR international corporations (VWR derived from Pennsylvania, America Xi Chesite International, West Chester, PA, USA) 0.2 micrometer polytetrafluoroethylene filter.Gained sample is injected into GPC In and eluted past with the speed of 1 ml/min and be maintained at 35 DEG C of post.System is calibrated with polystyrene standards, used Linear least square is analyzed to set up standard calibration curve.Dividing equally again for each sample is calculated according to the standards calibration curve Son amount (Mw) and polydispersity index (with weight average molecular weight divided by number-average molecular weight (Mn)).

Method of testing 2：Viscosity

Massachusetts, USA (is obtained from Brookfield viscosimeters with the rotating speed of 30 revs/min (rpm) using No. 3 rotors State Mead Er Baile Bo Lefei engineering companies (Brookfield Engineering, Middleboro, MA, USA)) measure Viscosity.

Method of testing 3：Weight of latex percentage (weight %) solid

In order to measure solids content, aluminium dish is weighed first, then about 0.2 gram to 0.3 gram of latex is added in disk. Latex is diluted by adding about 0.5 gram of deionized-distilled water.Disk is heated about 4 hours in 80 DEG C of baking ovens, until weight No longer change.The weight % (wt.% solids) of solid is calculated according to the following equation：

Weight % solid=100 × (W2-W1)/(W3-W1).

In the formula, W2 is the weight sum of weight and the dry polymer latex of disk, and W1 is the weight of disk, and W3 It is weight sum of the weight with wet polymer latex of disk.

Method of testing 4：Latex pH

With pH instrument, (with trade name, " MODEL 60A pH METER " derive from California, USA Luo Ling hills villa garden Chemtrix companies (Chemtrix, Rolling Hills Estates, CA, USA)) measure the pH of latex.

Method of testing 5：The glass transition (Tg) of polymer is measured by differential scanning calorimetry (DSC)

Dry polymer sample with go water removal and/or organic solvent.Then drying sample is weighed and loads TA instruments In Tzero (TA Instruments Tzero) DSC sample hermetic aluminum pans.Sample is analysis is carried out as follows：It is public using TA instruments (TA Instruments) Q2000 modulation systems differential scanning calorimetry (DSC) (" Q2000MDSC ", including RC-03761 sample cells) is taken charge of, Used in nitrogen atmosphere under temperature modulation pattern (- 90 DEG C to 125 DEG C, 5 DEG C/min, modulation amplitude is ± 0.796 DEG C, and Shi Changwei 60 seconds) heating-cooling-heating means.TA instrument companies (TA Instruments) are located at Delaware, USA knob Ka Sier (New Castle, DE, USA).

Under temperature modulation pattern, Q2000MDSC sends three kinds of signals：Accumulate (standard) hot-fluid, reverse (Rev) hot-fluid and Non- inverse (Nonrev) hot-fluid.Accumulation heat flow signal is reverse heat flow signal and non-backheating stream signal sum.Reverse signal is thermal capacitance (Cp) component is measured, the change of thermal capacity is presented and including transformation, such as Tg (glass transition).Non- inverse signal is power point Amount, and including power transformation, such as crystallize and chemically react.

Collect after data, heat deflection is analyzed using TA UNIVERSAL ANALYSIS programs.If there is Words, are estimated to any glass transition (Tg) or significant neither endothermic nor exothermic peak value.Glass transition temperature uses standard Hot-fluid (HF) or reverse hot-fluid (related Cp/REV HF) order of a curve transition are estimated.Record transformation initial temperature, in Point (half is high) temperature and outlet temperature, and calculate the thermal capacity change observed in glass transition.Any peak transformation It is estimated using hot-fluid (HF), reverse hot-fluid (Rev HF) or non-backheating stream (Nonrev HF) curve.Also determine peak area value And/or minimum/peak-peak temperature.By the peak value unified result normalization of example weight and it is reported as J/g.

Method of testing 6：Via the granularity of dynamic light scattering

Be less than 1 micron of polymeric dispersions (or latex) for particle mean size, with latex dilute sample (about In 5mL water one drop latex) dynamic light scattering instrument (ZETASIZER NANO ZS, the Malvern instrument from Britain Wu Site prefectures Device company (Malvern Instruments Ltd., Worcestershire, UK) obtains), according to the instruction of manufacturer, and make Calibrate standard to measure the particle mean size of rubber latex sample with polystyrene bead.

Method of testing 7：Via the granularity of laser diffraction

It is more than 1 micron of polymeric dispersions (or latex) for particle mean size, according to the instruction of manufacturer, with dilute Releasing latex sample, (in deionized water, the weight ratio of polymeric dispersions and 1%DS-10 surfactant solutions is about 1:5) The HORIBA LA-950 laser diffraction particle size analyzers (Horiba instrument companies (Horiba of kyoto, Japan Instruments, Inc., Kyoto, Japan)) particle mean size is measured by laser diffraction.

Method of testing 8：For 90 degree of peel adhesions test of polypropylene substrate

Contact adhesive sample to be tested is applied to the poly- of 2.0 mils (0.002 inch, about 51 microns) with hand spatula (HOSTAPHAN 3SAB, scribble the PET film of priming paint to ester film, public purchased from Mitsubishi's polyester film of South Carolina, United States Greer Take charge of (Mitsubishi Polyester Film Inc., Greer, SC, USA)) on, and it is dry 15 points in 70 DEG C of baking oven Clock is to form drying PSA of the thickness range as 0.9 to 1.2 mil (about 23 to 30 microns).By band coating film at 23 DEG C and Placed under conditions of 50% relative humidity about 24 hours, be then cut into 0.5 inch of (about 1.3cm) wide article tape.

Polypropylene (PP) test panel (5cm × 12.5cm panels, obtained from Minn. Burns Wei Er's Aeromat Plastics Companies (Aeromat Plastics, Burnsville, MN, USA)), it is prepared as follows：Use hand The paper handkerchief that pressure isopropanol soaked wipes panel 8 to 10 times.The clean paper handkerchief soaked with isopropanol repeats the flow More than twice.Cleaned panel is air-dried.

It is with the roller of 2 kilograms (4.5 pounds) that 0.5 inch (1.25cm) is wide first in order to carry out PP peel adhesion tests Article tape is coated in PP substrates.Then according in ASTM international standards D3330/D3330M-04 (2010 check and approve version again) method F Described process, peel test is carried out with 90 degree of removal angle.

(the limited public affairs of Ai Mashi of Massachusetts, United States Ah's Coudé are obtained from IMASS SP-2000 slips/peel test instrument Take charge of (IMASS, Inc., Accord MA, USA)), stripping is evaluated with the peeling rate of 305mm/ minutes (12 inch/minute) viscous Attached power.Peel adhesion values are shown with both ounce/inch (oz/in) and newton/decimetre (N/dm).

Method of testing 9：For the 180 degree peel adhesion test of stainless steel base

Contact adhesive sample to be tested is applied to the poly- of 2.0 mils (0.002 inch, about 51 microns) with hand spatula (HOSTAPHAN 3SAB, scribble the PET film of priming paint to ester film, public purchased from Mitsubishi's polyester film of South Carolina, United States Greer Take charge of (Mitsubishi Polyester Film Inc., Greer, SC, USA)) on, and it is dry 15 points in 70 DEG C of baking oven Clock is to form drying PSA of the thickness range as 0.9 to 1.2 mil (about 23 to 30 microns).By band coating film at 23 DEG C and Placed 24 hours under conditions of 50% relative humidity, be then cut into 0.5 inch of (about 1.3cm) wide article tape.

0.5 inch of (about 1.3cm) wide article tape is administered on stainless steel (SS) plate with 2kg (4.5 pounds) roller, so Afterwards (the Ai Mashi Co., Ltds of Massachusetts, United States Ah's Coudé are obtained from IMASS SP-2000 slips/peel test instrument (IMASS, Inc., Accord MA, USA)), come with the peel angle of 180 degree and the speed of (about 30cm) per minute 12 inches Evaluate peel adhesion.Peel adhesion values are shown with both ounce/inch (oz/in) and newton/decimetre (N/dm).

Method of testing 10：Static Shear Strength at 70 DEG C

According to ASTM international standards D3654/D3654M-06 (2011 check and approve version again)-flow A, it is being set as 70 DEG C of baking In case the Static Shear Strength of adhesive is determined using 500 grams of loads.Sample is prepared in the following way：Will be a piece of 0.5in × 1in (1.3cm × 2.5cm) adhesive or adhesive tape is laminated on polypropylene (PP) or stainless steel (SS) panel.To divide Clock is the time that adhesive is pulled away from panel by the time that unit records failure, i.e. counterweight.If do not observed after 10,000 minutes To failure, then the value for stopping testing and recording 10,000+ minutes.

Method of testing 11：The adhesion test that fabric is bonded

Fabric (is obtained for motion nylon with production code member 1997147 from Joann Fabrics companies (Joann Fabrics) , royalblue), fabric is cut into the bar that 1 inch (about 2.5cm) is wide and 6 inches (15.2cm) is long.Adhesive tape is cut into The bar that 0.5 inch (1.3cm) is wide and 7-8 inches (18 to 20cm) are long.Article tape is applied on fabric strip.With 2kg (4.5 pounds) Roller test sample is laminated together；Then 1 hour is stood before test.Then fabric end is put into Instron devices Lower jaw in, and adhesive tape end is put into upper jaw.It is following that Instron devices are set：Crosshead speed is 12 inch/minutes (30.5cm/min), and average load is between 2 inches (5.1cm) and 5 inches (12.7cm), and this part is in sample Between part.Three readings are recorded, are averaged, and be reported as peel adhesion.

Preparation example 1 (PE-1)

Polymer is prepared by two steps.In the first step of polymerization, in reactor (stirring-type stainless steel reaction Device) in add the mixture that is made up of following item：88kg IBOA and 2.72kg acrylic acid (AA) and 90.8 grams of IRGANOX 1010th, 381 grams of IOTG, 18.2 grams of MEHQ and 1.8 gram of VAZO 52.By reactor sealing and deoxidation, about 5psig is then maintained at Under the nitrogen pressure of (34.5kPa).Reactant mixture is heated to 60 DEG C (140 ℉), and carries out adiabatic reaction, and temperature peak For 127 DEG C (260 ℉).When the reactions are completed, mixture is cooled to less than 50 DEG C.

In the second step, 10.9 grams of VAZO 52,3.6 grams of VAZO 67,5.4 are added into the reaction product of first step (initiator component is to be dissolved in a small amount of ethyl acetate by gram VAZO 88,5.4 grams of LUPERSOL 101 and 7.3 grams of LUPERSOL 130 In solution be added).Then 191 grams of other IOTG are added.Reactor is sealed and purged with nitrogen, and is maintained at Under 5psig (34.5kPa) nitrogen pressure.Reactant mixture is heated to 60 DEG C (140 ℉), and carries out adiabatic reaction.Anti- After the peak temperature (350 ℉) that 176 DEG C should be reached, mixture is heated at this temperature 2 hours.The polymeric material of gained It is referred to as PE-1.In order to take out PE-1 from reactor, heating mantle is drained, and by addition EHA after 2 hours.Gained it is poly- Polymer solution includes the PE-1 being dissolved in added EHA, is then cooled to the polymer solution of gained 93 DEG C (200 ℉) And be stirred overnight.

As used herein, term " PE-1 " refers to the polymeric material formed by IBOA/AA (97/3), and its is heavy respectively Son amount is 35kg/ moles.PE-1 used below all formulations are based on the weight meter of polymer, without be based upon by PE-1 is dissolved in the weight meter of polymer solution formed by EHA.Added to formed the EHA of polymer solution by regarding For a part for the first monomer composition.

Preparation example 2 (PE-2)

(Illinois, America Bai Erleiji is purchased from using the VSP2 adiabatic reactions equipment equipped with 316 stainless steel test tanks Fauske and Associates companies (Fauske and Associates, Burr Ridge IL, USA)), pass through two Step reacts to be polymerize.

In the first step of polymerization, 80 grams of monomer mixture (IBOA/ are added in the test tank in VSP2 reactors AA:97/3 weight ratio).Added into monomer mixture 0.1pph IRGANOX 1010,2pph chain-transferring agent (IOTG), 0.02pph MEHQ and 0.002pph VAZO 52, wherein being based on the gross weight meter of monomer in monomer mixture per pph. Reactor is sealed and purged with nitrogen, under the nitrogen pressure for being then maintained at about 100psig (689kPa).By reactant mixture 60 DEG C are heated to, and carries out adiabatic reaction.General peak temperature is about 180 DEG C.Temperature is reached after peak value, and mixture is cold But to less than 50 DEG C.

In the second step, initiator solution is added in the reaction product of 75 grams of first step.Solution is included 0.012pph VAZO 52,0.004pph VAZO 67,0.006pph VAZO 88,0.006pph LUPERSOL 101, With 0.008pph LUPERSOL130, wherein being based on the weight meter of polymeric material in reaction product per pph.By initiator It is dissolved in a small amount of ethyl acetate, and initiator solution weighs 0.7 gram altogether.Then the IOTG (1pph) of additional amount is added. Reactor is sealed, deoxidation, and be maintained under 100psig (793kPa) nitrogen pressure.Reactant mixture is heated to 60 DEG C, and And adiabatic reaction is carried out, peak temperature is about 124 DEG C.Reactant mixture is heated to 170 DEG C and keeps 1 small at such a temperature When.Then polymer is cooled down.The polymer of gained has the composition that IBOA/AA is 97/3 and 8kg/mol Mw.

Preparation example 3 (PE-3)

Preparation and flow are identical with PE-2, the difference is that the amount and reaction peak temperature of chain-transferring agent are changed. In step 1,1.1pph IOTG is added, and peak temperature is about 134 DEG C.In step 2,0.55pph IOTG is added, and And peak temperature is about 138 DEG C.The polymer of gained has the composition that IOBA/AA is 97/3 and 14kg/mol Mw.

Preparation example 4 (PE-4)

Preparation and flow are identical with PE-2, the difference is that the amount and reaction peak temperature of chain-transferring agent are changed. In step 1,0.6ppph IOTG is added, and peak temperature is about 130 DEG C.In step 2,0.3pph IOTG is added, and And peak temperature is about 133 DEG C.The polymer of gained has the composition that IOBA/AA is 97/3 and 23kg/mol Mw.

Preparation example 5 (PE-5)

Into bottle add 150 grams ethyl acetate, 37.50 grams of IBOA, 11 grams of IBOMA, 1.50 grams of AA, 0.25 gram VAZO 67 and 0.125 gram of IOTG.Then purge reactant to remove oxygen with nitrogen.Then seal the bottle and put Put in 60 DEG C of launderometer (Launderometer) 24 hours.Then polymer solution is put into aluminium dish, and Dry to remove solvent in an oven.Dry polymer has the composition and about that IBOA/IBOMA/AA is 75/22/3 34kg/mol Mw.

Preparation example 6 (PE-6)

Polymer is carried out as follows preparation：According to patent application publication No.W0 96/07522 and United States Patent (USP) No.5,804, Method described in 610 (Hamer et al.), polymerisation in bulk is triggered in polymer pouches by ultraviolet radiation.Polymer passes through It is prepared by the preparation with following item：IOA (84.3pph), IBOA (12.7pph), AA (3pph), IOTG (0.03pph) and IRGACURE651(0.15pph).The gross weight meter of all monomers is based on per pph.Polymer has IOA/IBOA/AA The composition of (84.3/12.7/3) and about 625kg/mol Mw.

Preparation example 7 (PE-7)

Polymer is carried out as follows preparation：According to patent application publication No.W0 96/07522 and United States Patent (USP) No.5,804, Method described in 610 (Hamer et al.), polymerisation in bulk is triggered in polymer pouches by ultraviolet radiation.Polymer passes through It is prepared by the preparation with following item：IOA (97pph), AA (3pph), IOTG (0.03pph) and IRGACURE 651 (0.15pph).The gross weight meter of all monomers is based on per pph.Polymer has IOA/AA (97/3) composition and about 576kg/mol Mw.

Preparation example 8 (PE-8)

DS-10 (3.80 grams) and 225 grams of deionized waters are added in beaker and stirred to form the aqueous solution.By AA (9.5 grams), CBr4 (0.18 gram) and IBOA (180.5 grams) are added in single beaker and are sufficiently mixed to form oil phase.So 2 liters of resins of the backward mechanical agitator, condenser and nitrogen inlet tube that formula blade impeller is fallen back equipped with thermometer, with glass burn Aqueous phase and oil phase are poured into bottle.Then reactant mixture is stirred under with 300 revs/min (rpm) under a nitrogen blanket.Will Reactant is heated to 29 DEG C, then adds KPS (0.38 gram), Na2S2O5 (0.10 gram) and FeSO4.7H2O solution (0.0011 Gram, in the H2O for being dissolved in 0.5 gram).The reaction forms 48 DEG C of peak heat release temperature.After reaching exothermic peak, by reactant It is heated to 75 DEG C and is kept for 1.5 hours at this temperature.Then latex is cooled down, and filters to obtain the weight of solid 39 by garrha Measure the latex of about 126 nanometers of %, pH about 4.6, the centipoise of viscosity about 2,000 and average grain diameter.The emulsion polymer has IBOA/ AA (97/3) composition and 162kg/mol Mw.

Preparation example 9 (PE-9)

First, IBOA/AA (97/3) copolymer that Mw is about 34,000g/mol is carried out as follows preparation：According to patent application Announce No.W0 96/07522 and United States Patent (USP) No.5, the method described in 804,610 (Hamer et al.), in polymer pouches Polymerisation in bulk is triggered by ultraviolet radiation.Polymer is prepared by the preparation with following item：IBOA(97pph)、AA (3pph), IRGACURE 651 (1pph) and IOTG (0.75pph), wherein per gross weight meters of the pph based on monomer.

Then 50 grams of resulting polymers, 50 grams of toluene, 0.64 gram of TRITON X-100,0.115 gram of DS-4 are blended in one Rise to form oil phase.Aqueous phase is carried out as follows preparation：25 grams of water and 0.115 gram of DS-4 are mixed.By aqueous phase solution, then It is that oil-phase solution is added in 1L stainless steel watt woods blender.Mixture is blended 2 minutes to be consolidated in the case where high speed is set Body is that about 40 weight %, viscosity are 3960 centipoises and average grain diameter is about 2.9 microns of polymer emulsion.

Table 2：Preparation example (PE-1 to PE-9) and DIANAL polymer collect

PE-6 and PE-9 Tg is calculated using Fox formula, and uses modulated DSC to measure PE-1 to PE-5, DIANAL BR113 and DIANAL MB2543 Tg.

Preparation example 10 (PE-10)：Prepare shortwave UV solidification liners

By 70 weight % TEGO RC-902 and 30 weight % TEGO RC-711 blend coated to thick 50 microns Unprimed PET film substrate (be purchased from South Carolina, United States Greer polyester film company of Mitsubishi (Mitsubishi Polyester Film Inc., Greer, SC, USA)) side on, to form wet coating of the thickness less than 1.0 microns.Then By band coating film exposed to (the he Li Shi special lights of Hanau, Germany in nitrogen atmosphere and with the speed of 15.2 ms/min (mpm) Source company (Heraeus Noblelight, Hanau, Germany) manufactures) three 150W low-pressure mercuries of the peak intensity at 185nm In the output of neat lamp, padded with providing the shortwave UV solidifications with solidification insulation surfaces.Other information on the pad is visible In U.S. Patent Publication 2013/0059105 (Wright et al.).

Embodiment 1 (EX-1)

Aqueous phase is carried out as follows preparation：The HITENOL BC1025 and 208 grams of deionized water of 15.6 grams of mixing in beaker. Oil phase is carried out as follows preparation：The acrylic acid-2-ethyl caproite (EHA) of 267 grams of mixing, the different ice of 40.5 grams of acrylic acid in beaker Piece ester (IBOA), 5.7 grams of acrylic acid (AA), 3.8 grams of methacrylic acid (MAA) and 9.5 grams of preparation example 1 (PE-1) Polymer, until forming solution.For the sake of more understanding, PE-1 refers to the polymer formed by IBOA/AA (97/3).Containing molten The amount of EHA included in the PE-1 of solution polymer solution (is added to remove PE-1 EHA from the reactor for preparing it Amount) be included in added EHA total amount in (267 grams).326.5 grams of oil phase gross weight.Then oil phase is poured into aqueous phase simultaneously It is sufficiently mixed.In the stainless steel watt woods blender container that content is poured into 1 liter, and carried out in the case where high speed is set with blender 2 minutes homogenize.Then to mechanical agitator, condenser and the nitrogen that formula blade impeller is fallen back equipped with thermometer, with glass Mixture is poured into 2 liters of resin flasks of inlet tube.Then 0.4 gram of potassium peroxydisulfate (KPS) is added.Stirring reaction under a nitrogen blanket Mixture, and be heated to 60 DEG C and kept for 4 hours at 60 DEG C.Then temperature is increased to 80 DEG C and warm herein in 30 minutes Degree is lower to be kept for 1 hour.Then cool down latex and be filtered through garrha, to obtain EX-1 latex.Latex is EHA/IBOA/ AA/MAA/PE-1(84/13/2/1/3).PH is about 2.8.

Fig. 1 show the second heating (2H) in the cycle as the temperature funtion in nitrogen atmosphere EX-1 emulsion polymer Modulated DSC heat flow signal.

Embodiment 2 is to embodiment 5 (EX-2 to EX-5)

To prepare these latexes with EX-1 identicals preparation, identical mode (miniemulsion process), the difference is that using PE- 2 (being used for EX-2), PE-3 (being used for EX-3), PE-4 (being used for EX-4) and PE-5 (being used for EX-5) substitute PE-1.

Fig. 2 show the second heating (2H) in the cycle as the temperature funtion in nitrogen atmosphere EX-2 latex particles modulation Formula DSC heat flow signals.

Comparative example 1 and 2 (CE-1 and CE-2)

To prepare these latexes with EX-1 identicals preparation, identical mode (miniemulsion process), the difference is that using DIANAL BR113 (being used for CE-1) or DIANAL MB2543 (being used for CE-2) substitute PE-1.Different from PE-1, DIANAL MB2543 and DIANAL BR113 are not prepared by the monomer with ring structure.CE-1 and CE-2 solids content is about 60 weights Measure %.CE-1 viscosity is 270 centipoises, and CE-2 viscosity is 220 centipoises.CE-1 average grain diameter is about 413nm, and CE-2 average grain diameter is 426nm.

Comparative example 3 (CE-3)

With (miniemulsion process) prepares the latex in an identical manner with EX-1 identicals preparation, unlike with preparing Example 6 (PE-6) substitutes PE-1.The solid of gained latex is 60 weight %, and viscosity is 92 centipoises, and average grain diameter is 548nm.

Comparative example 4 (CE-4)

With (miniemulsion process) prepares the latex in an identical manner with EX-1 identicals preparation, unlike with preparing Example 7 (PE-7) substitutes PE-1.After polymerization, ammonia is added in latex, the pH of latex is adjusted to about 4.Gained latex is consolidated Body content is 58 weight %.

Comparative example 5 (CE-5)

According to preparing the latex with EX-1 identicals method, unlike both without PE-1 or without any other Preformed polymer.Polymerisation present invention thing condenses, and does not obtain any latex.

Table 3：EX-1 to EX-5 and CE-1 to CE-5 composition

CE-4 Tg is calculated using Fox formula, and uses modulated DSC to measure EX-1 to EX-5 and CE-1 to CE-3's Tg.N/A refers to because latex is not formed and is not analyzed.

Table 4：EX-1 to EX-5 and CE-1 to CE-4 adhesive properties

Comparative example 6 (CE-6)

By the CE-3 (60 weight % solids) that 30 grams of Tg are -50 DEG C and PE-8 (the 39 weight % that 1.43 grams of Tg are 95 DEG C Solid) blending.The weight ratio of CE-3 polymer and PE-8 polymer is 100 to 3 (100:3).The adhesive properties of blend Measured, and be shown in Table 5 using method of testing 8,9 and 10.

Comparative example 7 (CE-7)

By the CE-4 (58 weight % solids) that 30 grams of Tg are -50 DEG C and PE-9 (the 40 weight % that 1.3 grams of Tg are 95 DEG C Solid) blending.The weight ratio of CE-4 polymer and PE-9 polymer is 100 to 3 (100:3).The adhesive properties of blend make Measured, and be shown in Table 5 with method of testing 8,9 and 10.

Table 5：The comparison of CE-3, CE-4, CE-6, CE-7 and EX-1 adhesive properties

Embodiment 6 (EX-6)

Polymer latex sample (60% solid) in 30 grams of EX-1 is total to 0.22 gram of thickener of PARAGUM 500 It is mixed.Ammonium is added into mixture, pH is adjusted to about 9.

The polymer latex blend sample in EX-6 is applied in preparation example 10 (PE-10) with hand spatula spreader In the solidification insulation surfaces of release liner, 20 minutes are then dried in 70 DEG C of baking ovens to obtain the " transfer with latex psa layer Band ", the dry thickness of wherein latex psa layer is about 2 mils (0.002 inch, about 51 microns).

Embodiment 7 (EX-7)

By the polymer latex sample (60% solid) in 30 grams of EX-1 and 0.3 gram of thickener of PARAGUM 500 and 6.1 grams of SNOWTACK SE780G (55% solid) tackifier blendings.EX-1 dry polymers are about with drying the ratio between tackifier 100:20.The pH of the polymer latex blend of gained is adjusted to about 9.

The polymer latex blend sample in EX-7 is applied in preparation example 10 (PE-10) with hand spatula spreader In the solidification insulation surfaces of release liner, 20 minutes are then dried in 70 DEG C of baking ovens to obtain the " transfer with latex psa layer Band ", the dry thickness of the latex psa layer is about 2 mils (about 51 microns).

Fissility and the test of adhesiveness again, preparation EX-6 and EX-7 " transfer belt "

Aging and/or put under the conditions of one in three below condition of " transfer belt " sample of embodiment 6 and 7 Under the conditions of one in three below condition：

Condition 1：23 DEG C, 50% relative humidity, 24 hours.

Condition 2：23 DEG C, 50% relative humidity (RH), 24 hours；Then 32 DEG C, 90%RH, 48 hours；Then 23 DEG C, Balanced 1 hour under 50% relative humidity.

Condition 3：23 DEG C, 50% relative humidity, 24 hours；Then heating 48 is small in 70 DEG C of (the not controlled system of humidity) baking ovens When；Then balanced 1 hour under 23 DEG C, 50% relative humidity.

Undergo after conditions above step, the PET film that 25 microns (1.0 mils) are scribbled into priming paint is laminated to the breast through processing On glue psa layer, to form lamination test sample.The PET film for scribbling priming paint is prepared by applying sol-gel priming paint, colloidal sol-solidifying Glue priming paint is as described in Japan Patent No.J02200476-A, and further such as United States Patent (USP) No.5,204,219 (Van Ooij Et al.), described in European patent No.0301827B1 (Woo et al.) and European patent No.0372756 (Strobel et al.).

Peel adhesion values are by PET backing types by 180 ° of angles and with the speed of 30.5 cm per minutes (12 inch/minute) Adhesive tape solidifies the measured value of the power needed for being stripped down on liner from shortwave UV.IMASS SP2000 type peel test instruments (the IMASS companies (IMASS Corp., Accord, MA, USA) of Massachusetts, United States Ah's Coudé) is used to record peel adhesion Force value, it is summarized in table 6 as " fissility " value.

In order to determine adhesion values again, using isolation test (method of testing 11) by PET backing type adhesive tape samples from Stripped down on shortwave UV solidification liners, and the PET backing type adhesive tapes of gained are then coated to clean stainless steel faceplate Surface.PET backing type adhesive tape samples are entered against panel with the speed of 61 cm per minutes (24 inch/minute) with 2kg rubber rollers Row is rolled twice.Adhesion values are by PET backings by 180 ° of angles and with the speed of 30.5 cm per minutes (12 inch/minute) again Type adhesive tape torn it down from surface of steel plate needed for power measured value.IMASSSP2000 types peel test instrument, which is used to record, to be peeled off Power, it is summarized in table 6 as " adhesion again " value.

Table 6：Transfer carry sample EX-6 and EX-7 performance

B applies example 8 (EX-8)

The latex of embodiment 1 (EX-1) is applied to 1 mil (0.001 inch, 0.0025cm) with hand spatula spreader Scribble on the PET film of priming paint, Sol-gel type priming paint of the PET film by coating as described in Japan Patent No.J02200476-A And prepare.Latex is dried 20 minutes to obtain drying of the thickness as 2 mils (0.002 inch, 0.005cm) in 70 DEG C of baking ovens Adhesive.After being placed 24 hours in constant temperature and constant humidity (23 DEG C and 50% relative humidity) room, tested using fabric adhesion (method of testing 11) is assessed PSA, is as a result shown in Table 7.

Embodiment 9 (EX-9)

The latex of embodiment 2 (EX-2) is applied to 1 mil (0.001 inch, 0.0025cm) with hand spatula spreader Scribble on the PET film of priming paint, Sol-gel type priming paint of the PET film by coating as described in Japan Patent No.J02200476-A And prepare.Latex is dried 20 minutes to obtain drying of the thickness as 2 mils (0.002 inch, 0.005cm) in 70 DEG C of baking ovens Adhesive.After being placed 24 hours in constant temperature and constant humidity (23 DEG C and 50% relative humidity) room, tested using fabric adhesion (method of testing 11) is assessed PSA, is as a result shown in Table 7.

Table 7：Fabric bond samples EX-8 and EX-9 performance

" fabric bonding " sample	The peel adhesion that fabric is bonded, oz/in (N/dm)
		EX-8	10.6(11.6)
EX-9	10.9(11.9)

Claims

1. a kind of emulsion compositions, the emulsion compositions are included：

A) water；

B) polymerisable surfactant, the polymerisable surfactant has the unsaturated group that may occur from being polymerize by base；

C) the first monomer composition, first monomer composition is included

1) straight or branched alkyl group has (methyl) alkyl acrylate of at least six carbon atoms；And

D) second (methyl) acrylate polymer, based on the gross weight meter of monomer in first monomer composition, described The amount of two (methyl) acrylate polymers is 0.5 weight % to 15 weight %, wherein described second (methyl) acrylate is poly- The Tg of compound is more than or equal to 50 DEG C, and wherein described second (methyl) acrylate polymer is by including the second of following item Monomer composition is formed

1) gross weight meter based on monomer in the second comonomer composition, at least 50 weight % (methyl) acrylate Ester, wherein the group of naphthene base has at least six carbon atoms；

Wherein

The emulsion has the first phase and the second phase, and described first mutually includes the water, and described second exists as droplet distribution In first phase；And

The drop includes the mixture for including following item：

1) described second (methyl) acrylate polymer；And

2) at least 90 weight % first monomer composition, wherein second (methyl) acrylate polymer with it is described First phase can not be miscible, and is dissolved in first monomer composition in the drop.

2. emulsion compositions according to claim 1, wherein first monomer composition also includes (methyl) acrylic acid Cycloalkanes ester, polar monomer, or both.

3. the latex composition according to claim 1 or claim 2, wherein first monomer composition includes 60 weights Measuring % has (methyl) alkyl acrylate, the 1 weight % of at least six carbon atoms to 98 weight % straight or branched alkyls groups To 30 weight % (methyl) acrylate ester and 1 weight % to 10 weight % the polar monomer.

4. emulsion compositions according to any one of claim 1 to 3, wherein the second comonomer composition includes 50 weights Measure % to 100 weight % (methyl) acrylate ester and 0 weight % to 50 weight % optional monomers, the optional list Body is for polar monomer, (methyl) alkyl acrylate with straight or branched alkyl group and without (methyl) acryloyl The vinyl monomer of group, (methyl) acrylamide, (methyl) acrylonitrile, N- alkyl (methyl) acrylamide, N, N- dialkyl group (methyl) acrylamide or their mixture.

5. emulsion compositions according to any one of claim 1 to 4, wherein the second comonomer composition includes 90 weights Measure the polar monomer of (methyl) acrylate ester and 0 weight % to 10 weight % described in % to 100 weight %.

6. emulsion compositions according to any one of claim 1 to 5, wherein first monomer composition is different from institute State second comonomer composition.

7. the emulsion compositions according to any one of claim 1 to claim 6, wherein described second (methyl) propylene The weight average molecular weight of acid ester polymer is in the range of 3,000 to 150,000 grams/mol.

8. the emulsion compositions according to any one of claim 1 to claim 7, wherein the emulsion does not include thickening Agent.

9. a kind of latex composition, the latex composition includes Emulsion combination according to any one of claim 1 to 8 The polymerizate of thing, wherein the latex composition includes polymeric latex particles.

10. latex composition according to claim 9, wherein as determined using differential scanning calorimetry (DSC), the polymerization Latex particle has single glass transition temperature.

11. the latex composition according to claim 9 or 10, wherein second (methyl) acrylate polymer and The polymerizate of first monomer composition is in the identical polymer particles together.

12. the latex composition according to any one of claim 8 to claim 11, is also viscosified comprising water-dispersion type Agent.

13. a kind of contact adhesive, the contact adhesive includes the latex group according to any one of claim 9 to 12 The desciccate of compound.

14. a kind of product, the product includes：

A) substrate；And

B) the first pressure sensitive adhesive layer, first pressure sensitive adhesive layer is positioned adjacent to the first main surface of the substrate, wherein First pressure sensitive adhesive layer includes contact adhesive according to claim 13.

15. a kind of method for forming contact adhesive, methods described includes

A) emulsion compositions according to any one of claim 1 to claim 8 are formed；

B) the emulsion compositions polymerization is made to form the latex composition for including emulsion polymerization particle；And

C) latex composition is dried to form the contact adhesive.